CN109622006B - Catalyst for preparing low-grade aliphatic amine from ammonia-containing synthesis gas and preparation method thereof - Google Patents
Catalyst for preparing low-grade aliphatic amine from ammonia-containing synthesis gas and preparation method thereof Download PDFInfo
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Abstract
A catalyst for preparing low-grade aliphatic amine from ammonia-containing synthetic gas is a supported Fe-Cu catalyst prepared by taking a nitrogen-doped carbon material as a carrier, and comprises the following components in percentage by weight: iron: 10.0-25.0 wt%; copper: 1.1-19.0 wt%; a nitrogen-doped carbon material carrier: 56.0-88.9 wt%. The invention greatly improves the amination reaction efficiency, the conversion rate of ammonia in the ammonia-containing synthetic gas is not less than 80.0 percent, and C is not less than C2‑C6Fatty amine selectivity ≧ 50.0wt%, C6 +The selectivity of the fatty amine is less than or equal to 5.0 wt%.
Description
Technical Field
The invention relates to a catalyst for synthesizing lower aliphatic amine and a preparation method thereof, in particular to a catalyst for selectively synthesizing lower aliphatic amine by catalyzing ammonia-containing synthesis gas and a preparation method thereof.
Technical Field
The aliphatic amine being ammonia (NH)3) The product of which one or more hydrogen atoms are replaced by alkyl is widely applied in the fields of medicine, agriculture, water treatment, rubber, solvent, surfactant and the like, and is an important chemical closely related to daily production and life.
From the fatty amine industry, higher fatty amines (C)6 +Mainly refers to C8～C24) The natural fatty acid is used as a hydrocarbon-based precursor, the production technology is mature, and the higher fatty amine is a basic chemical product of the grease chemical industry. Lower aliphatic amine (C)1～C6) By amination of alcohols or olefins with the corresponding hydrocarbon radicals (e.g. the lower aliphatic amine production process disclosed in patent CN201010291756.8 starting from the corresponding alcohols, ketones) Or by ammonolysis of halogenated hydrocarbons (e.g. patent CN201710467963.6 discloses a process for the preparation of lower aliphatic amines by bromination-ammonolysis of lower alkanes), especially C2 +The product not only has complex amination reaction process or poor atom economy, but also has hydrocarbon group source related to a plurality of intermediate processes such as synthesis, purification and the like. Therefore, the need for innovation of the synthesis technology of lower aliphatic amines is urgent.
The one-step synthesis of fatty amine from ammonia-containing synthesis gas is a process of directly obtaining a target product by taking synthesis gas and ammonia as raw materials through hydrogenation and amination reactions. Compared with the existing fatty amine synthesis method, the process for preparing the fatty amine does not need to synthesize a hydrocarbon-based precursor in advance.
The research of reaction mechanism shows that the initiation and growth mode of the hydrocarbon carbon chain of the synthetic gas and the synthesis of fatty amine by ammonia are the same as the reaction of synthesizing hydrocarbon and alcohol by CO hydrogenation, and the main problems are as follows: the yield of the fatty amine is low, and the regulation and control difficulty of the product is large. Patents CN00123366.1 and CN0012362.9 adopt copper-based and chromium-based catalysts respectively to catalyze ammonia-containing synthesis gas to prepare lower aliphatic amine, but because there is no carbon chain growth center, the obtained product is mainly methylamine and almost no C2 +And (4) generating fatty amine. Patents US 3726926, US 2518754, US 4250116 try to improve the chain growth ability by using Fe-based catalysts, but the reaction products not only contain a large amount of hydrocarbon by-products such as alkanes and alkenes, but also fatty amines are distinguished according to the number of carbons of the hydrocarbon group, the types are dozens of, the separation is difficult, and part of organic amines have no application value, thus affecting the overall economy of the process.
Disclosure of Invention
The invention aims to provide a catalyst C with high ammonia conversion rate2-C6In the range of catalyst for preparing low-grade fatty amine from ammonia-containing synthesis gas with high fatty amine selectivity and a preparation method thereof.
Aiming at the intrinsic reaction characteristic of synthesizing the lower aliphatic amine by ammonia-containing synthesis gas, the invention designs the lower aliphatic amine (C) by starting from the control of the length of a carbon chain of a hydrocarbyl group, the activation of ammonia and the synergy of the two1-C6) Synthesizing a catalyst: the framework N in the nitrogen (N) -doped carbon material carrier is used for continuously restraining the iron, the carbon chain growth capacity of the iron is weakened, and surface electronegative iron particles are constructedAnd (4) granulating. The method comprises the steps of depositing copper on the surface of iron particles in a directional mode by metal copper under the action of electrostatic induction, enhancing amination reaction by utilizing proper activation capacity of copper on ammonia, completing construction of copper/iron adjacent distribution structures and controllable dispersion of copper/iron composite particles on a C-N carrier, and further preparing the efficient catalyst for preparing low-grade aliphatic amine from ammonia-containing synthetic gas.
The catalyst of the invention specifically takes nitrogen-doped carbon material as a carrier to prepare the supported Fe-Cu catalyst. The catalyst comprises the following components in percentage by weight:
iron: 10.0-25.0 wt%;
copper: 1.1-19.0 wt%;
a nitrogen-doped carbon material carrier: 56.0 to 88.9wt%
The nitrogen-doped carbon material is a porous carbon material with the content of N element of 0.5-5.5wt%, wherein the specific surface area of the nitrogen-doped carbon material carrier is 400-2G, average pore diameter of 2-10 nm. .
The nitrogen-doped carbon material carrier belongs to a porous nitrogen-doped carbon-based material, and can be selected from the existing commercial nitrogen-doped carbon materials, such as nitrogen-doped porous activated carbon, nitrogen-doped graphene, nitrogen-doped mesoporous carbon and the like.
One feature of the catalyst described above is that metallic iron is deposited on the nitrogen sites of the nitrogen-doped carbon material, and copper is subsequently deposited on the surface of the resulting iron particles. The relative positions of copper, iron and carrier are shown in FIG. 1.
The catalyst of the invention is prepared according to the following steps:
(1) preparing an iron salt solution with the concentration of 0.2-1.0mol/L and a copper salt solution with the concentration of 0.2-1.0mol/L according to the composition of the catalyst;
(2) under the condition of stirring, dispersing the nitrogen-doped carbon material carrier in ferric salt solution, depositing iron on nitrogen sites of the nitrogen-doped carbon carrier by using a chemical reduction method under the protection of inert atmosphere, washing the obtained sample to be neutral,
(3) re-dispersing the neutral sample in deionized water (the amount of the deionized water is the same as the volume of the ferric salt solution), stirring, dropwise adding the copper salt solution, continuously stirring for 2-12h after dropwise adding, reacting the copper ions with iron deposited on the carrier under electrostatic attraction, depositing the copper ions on the surfaces of iron particles, filtering and washing until the filtrate is neutral, drying the obtained solid sample at 50-120 ℃, roasting at 350-650 ℃ in an inert atmosphere, and reducing at 350-650 ℃ in a hydrogen-containing atmosphere to obtain the catalyst.
The ferric salt solution is prepared by dissolving water-soluble ferric salt in deionized water; after the water-soluble iron salt is dissolved in water, the iron can be taken as a cation (Fe)2+、Fe3+Or both) form. The water soluble ferric salt is preferably ferric nitrate, ferric chloride, ferrous chloride, or ferrous acetate.
The copper salt is prepared by dissolving water-soluble copper salt in deionized water; said water-soluble copper salt, after being dissolved in water, can be selected from the group consisting of Cu2+The form exists. The water-soluble copper salt is preferably copper nitrate, copper chloride, copper acetate, or the like.
Chemical reduction process as described above: preparing a sodium borohydride solution, dropwise adding the sodium borohydride solution into the ferric salt solution dispersed with the nitrogen-doped carbon carrier, and reacting at normal temperature until the reaction is complete;
the concentration of the sodium borohydride solution is 0.5-5.0% by mass of the sodium borohydride, and the mass ratio of the sodium borohydride to the iron is 1-5.
The hydrogen-containing atmosphere as described above means hydrogen, or a mixed gas of hydrogen and an inert atmosphere, in which the hydrogen content is not less than 30.0 vol%.
The inert gas in the inert atmosphere as described above refers to a gas such as nitrogen, argon, or helium.
Compared with the existing fatty amine synthesis route, the synthesis of the fatty amine by the ammonia-containing synthesis gas is a new fatty amine synthesis route, and not only relates to the substitution of hydrogen atoms on ammonia molecules, but also comprises the initiation and growth processes of hydrocarbon-based carbon chains. The aliphatic amine is prepared by the process without synthesizing a hydrocarbon-based precursor in advance. Compared with the existing ammonia-containing synthesis gas catalytic conversion route, the catalyst provided by the invention has the advantages that:
(1) by utilizing electron transfer from nitrogen in nitrogen-iron to iron direction, electronegative iron particles on the surface are constructed, then iron is directionally deposited on the electronegative iron particles, an iron/copper adjacent structure is constructed, the amination reaction efficiency is greatly improved, and the ammonia conversion rate of ammonia-containing synthetic gas is not less than 80.0%;
(2) the restraint effect of nitrogen element in the carbon material on iron is utilized to reduce the chain growth capacity of iron in the CO hydrogenation reaction, so that a low-carbon aliphatic amine product C urgently needed by the industry is selectively generated2-C6Fatty amine selectivity ≧ 50.0wt%, C6 +The selectivity of the fatty amine is less than or equal to 5.0 wt%.
Drawings
FIG. 1 is a diagram showing the relative positions of copper, iron and a carrier in a target catalyst.
Detailed Description
Several illustrative, but non-limiting examples are given below.
Example 1:
with a specific surface area of 976.0m2The nitrogen-doped graphene with the average pore diameter of 2.9nm and the N element content of 0.5 wt% is used as a carrier, and the dosage of the carrier is 88.90 g. 43.31g of ferric nitrate (as Fe (NO))3)3Calculated), 1.0mol/L ferric nitrate aqueous solution is prepared. 3.15g of copper acetate (in C) are weighed out4H6CuO4Calculated), 0.2mol/L copper acetate aqueous solution is prepared. Preparing 0.5 wt% of sodium borohydride aqueous solution, wherein the molar ratio of sodium borohydride to iron in the ferric salt is 1: 1 calculating the solution dosage.
And dispersing the nitrogen-doped graphene in the ferric salt solution under the stirring condition. Under the protection of nitrogen atmosphere, dropwise adding a sodium borohydride solution into the mixture, and reacting at normal temperature until the mixture is complete. After washing the sample to neutrality, the sample is re-dispersed in deionized water (the amount of deionized water is the same as the volume of the ferric salt solution), and stirred. The copper salt solution was added dropwise. After the dropwise addition, stirring is continued for 6h, and copper ions react with iron deposited on the carrier under electrostatic attraction, so that the copper ions are deposited on the surface of the iron particles. The solid sample was filtered and washed until the filtrate was neutral. Drying the obtained sample at 60 ℃, and then roasting at 400 ℃ under the protection of argon atmosphere; and then reducing the mixture at 450 ℃ in a pure hydrogen atmosphere to obtain the target catalyst. The catalyst comprises the following components: Fe/Cu/nitrogen-doped carrier 10.00 wt%/1.10 wt%/88.90 wt%.
Example 2:
with a specific surface area of 856.0m2The carrier is commercial nitrogen-doped porous active carbon with the volume of 79.00g, the average pore diameter of 5.5nm and the content of N element of 2.5wt percent. 46.47g of ferric chloride (in FeCl) was weighed out3Calculated), 0.8mol/L ferric chloride aqueous solution is prepared. 14.77g of copper nitrate (in Cu (NO) was weighed out3)2Calculated), 0.8mol/L of copper nitrate aqueous solution is prepared. Preparing 1.0 wt% of sodium borohydride aqueous solution, wherein the molar ratio of sodium borohydride to iron in the ferric salt is 2: 1 calculating the solution dosage.
Under the stirring condition, nitrogen-doped porous activated carbon is dispersed in iron salt solution. Under the protection of argon atmosphere, dropwise adding a sodium borohydride solution into the mixture, and reacting at normal temperature until the mixture is complete. After washing the sample to neutrality, the sample is re-dispersed in deionized water (the amount of deionized water is the same as the volume of the ferric salt solution), and stirred. The copper salt solution was added dropwise. After the dropwise addition, stirring is continued for 4h, and copper ions react with iron deposited on the carrier under electrostatic attraction, so that the copper ions are deposited on the surface of the iron particles. The solid sample was filtered and washed until the filtrate was neutral. Drying the obtained sample at 90 ℃, and then roasting at 550 ℃ under the protection of argon atmosphere; and then reducing the mixture at 400 ℃ in the atmosphere of hydrogen-argon mixed gas with the hydrogen content of 50.0 vol% to obtain the target catalyst. The catalyst comprises the following components: Fe/Cu/nitrogen-doped carrier 16.00 wt%/5.00 wt%/79.00 wt%.
Example 3:
with a specific surface area of 770.0m2The carrier is commercial nitrogen-doped porous activated carbon which is used as the carrier, wherein the carrier is 56.00g, the average pore diameter is 3.4nm, and the content of N element is 2.8 wt%. 56.74g of ferrous chloride (in FeCl) were weighed out2Metering), preparing a 0.5mol/L ferrous chloride aqueous solution. 40.23g of copper chloride (in CuCl) are weighed out2Calculated), 0.3mol/L aqueous solution of copper chloride is prepared. Preparing 0.5 wt% of sodium borohydride aqueous solution, wherein the molar ratio of sodium borohydride to iron in the ferric salt is 3: 1 calculating the solution dosage.
Under the stirring condition, nitrogen-doped porous activated carbon is dispersed in iron salt solution. Under the protection of helium atmosphere, dropwise adding sodium borohydride solution into the mixture, and reacting at normal temperature until the mixture is complete. After washing the sample to neutrality, the sample is re-dispersed in deionized water (the amount of deionized water is the same as the volume of the ferric salt solution), and stirred. The copper salt solution was added dropwise. After the dropwise addition, stirring is continued for 6h, and copper ions react with iron deposited on the carrier under electrostatic attraction, so that the copper ions are deposited on the surface of the iron particles. The solid sample was filtered and washed until the filtrate was neutral. Drying the obtained sample at 50 ℃, and then roasting at 350 ℃ under the protection of argon atmosphere; and then reducing the mixture at 350 ℃ in the atmosphere of hydrogen-argon mixed gas with the hydrogen content of 45.0 vol% to obtain the target catalyst. The catalyst comprises the following components: Fe/Cu/nitrogen-doped carrier 25.00 wt%/19.00 wt%/56.00 wt%.
Example 4:
with a specific surface area of 542.0m2The carrier is commercial nitrogen-doped porous active carbon with the volume of 65.00g, the average pore diameter of 9.6nm and the content of N element of 3.4 wt%. 71.63g of ferrous acetate are weighed out (as C)4H6O4Calculated as Fe), preparing a ferrous acetate acid water solution of 0.2 mol/L. 35.44g of copper nitrate (in Cu (NO) is weighed out3)2Calculated), a 0.9mol/L aqueous solution of copper nitrate was prepared. Preparing 1.0 wt% of sodium borohydride aqueous solution, wherein the molar ratio of sodium borohydride to iron in the ferric salt is 5: 1 calculating the solution dosage.
Under the stirring condition, nitrogen-doped porous activated carbon is dispersed in iron salt solution. Under the protection of helium atmosphere, dropwise adding sodium borohydride solution into the mixture, and reacting at normal temperature until the mixture is complete. After washing the sample to neutrality, the sample is re-dispersed in deionized water (the amount of deionized water is the same as the volume of the ferric salt solution), and stirred. The copper salt solution was added dropwise. After the dropwise addition, stirring is continued for 7h, and copper ions react with iron deposited on the carrier under electrostatic attraction, so that the copper ions are deposited on the surface of the iron particles. The solid sample was filtered and washed until the filtrate was neutral. Drying the obtained sample at 100 ℃, and then roasting at 650 ℃ under the protection of helium atmosphere; and then reducing the mixture at 650 ℃ in a hydrogen-helium mixed gas atmosphere with the hydrogen content of 60.0 vol% to obtain the target catalyst. The catalyst comprises the following components: Fe/Cu/nitrogen-doped carrier 23.00 wt%/12.00 wt%/65.00 wt%.
Example 5:
with a specific surface area of 410.0m2The carrier is commercial nitrogen-doped mesoporous carbon with the volume of 75.5g, the average pore diameter of 7.2nm and the N element content of 4.2 wt%. 71.46g of ferric nitrate (in terms of Fe (NO) were weighed out3)3Calculated), 0.9mol/L ferric nitrate aqueous solution is prepared. 16.94g of copper chloride (in CuCl) are weighed out2Calculated), 0.7mol/L aqueous solution of copper chloride is prepared. Preparing 2.0 wt% of sodium borohydride aqueous solution, wherein the molar ratio of sodium borohydride to iron in the ferric salt is 4: 1 calculating the solution dosage.
Under the condition of stirring, the nitrogen-doped mesoporous carbon is dispersed in the ferric salt solution. Under the protection of helium atmosphere, dropwise adding sodium borohydride solution into the mixture, and reacting at normal temperature until the mixture is complete. After washing the sample to neutrality, the sample is re-dispersed in deionized water (the amount of deionized water is the same as the volume of the ferric salt solution), and stirred. The copper salt solution was added dropwise. After the dropwise addition, stirring is continued for 2h, and copper ions react with iron deposited on the carrier under electrostatic attraction, so that the copper ions are deposited on the surface of the iron particles. The solid sample was filtered and washed until the filtrate was neutral. Drying the obtained sample at 120 ℃, and then roasting at 600 ℃ under the protection of argon atmosphere; then reducing the mixture at 450 ℃ in the atmosphere of hydrogen-argon mixed gas with the hydrogen content of 30.0vol% to obtain the target catalyst. The catalyst comprises the following components: Fe/Cu/nitrogen-doped carrier 16.50 wt%/8.00 wt%/75.50 wt%.
Example 6:
with a specific surface area of 623.0m2The carrier is commercial nitrogen-doped porous active carbon which is used as per gram, has the average pore diameter of 5.4nm and the N element content of 5.5wt percent, and the dosage of the carrier is 60.0 g. 72.61g of ferric chloride (in FeCl) was weighed out3Calculated), 1.0mol/L ferric chloride aqueous solution is prepared. 44.31g of copper nitrate (in Cu (NO) was weighed out3)2Calculated), 1.0mol/L of copper nitrate aqueous solution is prepared. Preparing 5.0wt% of sodium borohydride aqueous solution, wherein the molar ratio of sodium borohydride to iron in the ferric salt is 2: 1 calculating the solution dosage.
Under the stirring condition, nitrogen-doped porous activated carbon is dispersed in iron salt solution. Under the protection of helium atmosphere, dropwise adding sodium borohydride solution into the mixture, and reacting at normal temperature until the mixture is complete. After washing the sample to neutrality, the sample is re-dispersed in deionized water (the amount of deionized water is the same as the volume of the ferric salt solution), and stirred. The copper salt solution was added dropwise. After the dropwise addition, stirring is continued for 12h, and copper ions react with iron deposited on the carrier under electrostatic attraction, so that the copper ions are deposited on the surface of the iron particles. The solid sample was filtered and washed until the filtrate was neutral. Drying the obtained sample at 110 ℃, and then roasting at 450 ℃ under the protection of nitrogen atmosphere; then reducing at 450 ℃ in the atmosphere of hydrogen-nitrogen mixed gas with the hydrogen content of 70.0 vol% to obtain the target catalyst. The catalyst comprises the following components: Fe/Cu/nitrogen-doped carrier 25.00 wt%/15.00 wt%/60.00 wt%.
Evaluation of catalyst:
the prepared catalyst samples were evaluated under typical reaction conditions, and the reaction results are shown in table 1. The raw material gas is H2CO and NH3Are formed jointly, wherein H2Mole ratio of/CO 2/1, NH3The content is 5.0 vol%, the reaction temperature is 280 ℃, the reaction pressure is 2.0MPa, and the GHSV is 3000h-1。
Table 1 evaluation results of catalyst samples
Claims (10)
1. A preparation method of a catalyst for preparing lower aliphatic amine from ammonia-containing synthesis gas is characterized in that the catalyst takes nitrogen-doped carbon material as a carrier to prepare a supported Fe-Cu catalyst, and the catalyst comprises the following components in percentage by weight: iron: 10.0-25.0 wt%; copper: 1.1-19.0 wt%; a nitrogen-doped carbon material carrier: 56.0-88.9 wt%; the nitrogen-doped carbon material carrier is a porous carbon material with the N element content of 0.5-5.5 wt%; the specific surface area of the nitrogen-doped carbon material carrier is 400-900m 2/g, and the average pore diameter is 2-10 nm; the nitrogen-doped carbon material carrier is nitrogen-doped porous activated carbon, nitrogen-doped graphene or nitrogen-doped mesoporous carbon; the method comprises the following steps:
(1) preparing an iron salt solution with the concentration of 0.2-1.0mol/L and a copper salt solution with the concentration of 0.2-1.0mol/L according to the composition of the catalyst;
(2) under the condition of stirring, dispersing the nitrogen-doped carbon material carrier in an iron salt solution, depositing iron on nitrogen sites of the nitrogen-doped carbon carrier by using a chemical reduction method under the protection of inert atmosphere, and washing the obtained sample to be neutral;
(3) and dispersing the neutral sample in deionized water again, wherein the volume of the deionized water is the same as that of the ferric salt solution, dropwise adding the cupric salt solution under stirring, continuously stirring for 2-12h after dropwise adding, filtering and washing until the filtrate is neutral, drying the obtained solid sample at 50-120 ℃, roasting at 350-650 ℃ under an inert atmosphere, and reducing at 350-650 ℃ under a hydrogen-containing atmosphere to obtain the catalyst.
2. The method of claim 1, wherein the ferric salt solution is prepared by dissolving a water-soluble ferric salt in deionized water, and the iron can be Fe after the water-soluble ferric salt is dissolved in water2+、Fe3+Or both together.
3. The method of claim 2, wherein the water-soluble ferric salt is ferric nitrate, ferric chloride, ferrous chloride or ferrous acetate.
4. The method of claim 1, wherein the copper salt solution is prepared by dissolving a water-soluble copper salt in deionized water; water-soluble copper salts after dissolution in water, the copper can be Cu2+The form exists.
5. The method of claim 4, wherein the water-soluble copper salt is one of cupric nitrate, cupric chloride, and cupric acetate.
6. The method of claim 1, wherein the chemical reduction comprises preparing a sodium borohydride solution, adding dropwise the sodium borohydride solution to the ferric salt solution dispersed with the nitrogen-doped carbon carrier, and reacting at room temperature to completion.
7. The method for preparing the catalyst for preparing the lower aliphatic amine from the ammonia-containing synthesis gas as claimed in claim 6, wherein the concentration of the sodium borohydride solution is 0.5-5.0% by mass of sodium borohydride, and the mass ratio of the amount of sodium borohydride to the amount of iron used is 1-5.
8. The method according to claim 1, wherein the hydrogen-containing atmosphere is hydrogen or a mixture of hydrogen and an inert atmosphere, and the hydrogen content is greater than or equal to 30.0 vol%.
9. The method according to claim 8, wherein the inert atmosphere is nitrogen, argon or helium.
10. The application of the catalyst prepared by the preparation method of the catalyst for preparing the lower aliphatic amine from the ammonia-containing synthesis gas as claimed in claim 1, wherein the catalyst is applied to synthesis of the aliphatic amine from the ammonia-containing synthesis gas.
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