CN107233887B - Preparation method and application of catalyst for synthesizing toluenediamine by hydrogenating dinitrotoluene - Google Patents
Preparation method and application of catalyst for synthesizing toluenediamine by hydrogenating dinitrotoluene Download PDFInfo
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- CN107233887B CN107233887B CN201710431010.4A CN201710431010A CN107233887B CN 107233887 B CN107233887 B CN 107233887B CN 201710431010 A CN201710431010 A CN 201710431010A CN 107233887 B CN107233887 B CN 107233887B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
A catalyst for synthesizing toluene diamine by hydrogenating dinitrotoluene is prepared by adding an additive into dried laterite-nickel ore powder, uniformly mixing, carrying out reduction magnetization, carrying out magnetic separation on the reacted and magnetized ore powder by a wet fine mill, and carrying out reduction activation to obtain the hydrogenation catalyst. The invention has the advantages of simple preparation, low cost and long service life.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a catalyst for synthesizing toluenediamine by hydrogenating dinitrotoluene.
Background
Aromatic amino compounds are important chemical raw materials and chemical intermediates in the chemical industry, and aniline, toluenediamine, chloronitroaniline, toluidine and the like are common. The source of the aromatic amino compound is derived in large part from the reduction of the nitro group of the corresponding nitrobenzene compound. As the nitro compound hydrogenation catalyst which is industrially used, supported noble metals (Pd/C, Pt/C, etc.) and amorphous alloys (Ni-B, Co-B, etc.) are mainly used. The supported noble metal catalysts such as palladium, rhodium, platinum and the like have higher activity in the hydrogenation reaction of nitrobenzene compounds, but have high production and application cost and are easy to deposit carbon and deactivate. The amorphous alloy catalyst is usually prepared by a chemical reduction method, and the reaction process is complex, so that the amorphous alloy catalyst is not beneficial to large-scale production and application.
Patent CN 1803761a reports a method for synthesizing aniline by hydrogenation of nitrobenzene at low temperature, in which the nitrobenzene hydrogenation temperature is 30-100 ℃, and the aniline yield under optimized conditions can reach 99.9%, but the method uses supercritical carbon dioxide as a reaction medium, the reaction pressure is high, the catalyst is a supported palladium catalyst, and the supercritical reaction conditions and noble metal catalyst increase the reaction cost. Patent document CN 105413693a reports a magnetically recoverable p-chloronitrobenzene hydrogenation reduction catalyst and a preparation method thereof, wherein in the preparation process, firstly, superoxide is used for preparing Fe3O4Nanometer magnetic ion, mixing with water soluble cobalt salt, reducing with sodium borohydride or potassium borohydride or other reducing agent under inert gas protection, washing, and drying to obtain the desired Co/Fe3O4Catalysts, but the catalysts prepared by this process are based on Fe3O4As carrier, peroxide KO is used2The preparation of the reaction is carried out in advance, and the reducing process of the reducing agent is a strong exothermic process and needs to be controlled. Patent document CN 102728363a adopts metallic iron as a reducing agent to reduce soluble nickel salt to prepare a ferronickel bimetallic catalyst, which shows good catalytic activity in dinitrotoluene hydrogenation reaction, but because the catalyst has the problem of difficult loading, the specific surface area is small, and the mechanical strength is poor.
Disclosure of Invention
Aiming at the problems of high preparation cost and complex preparation process of the traditional hydrogenation catalyst, the invention provides a preparation method and application of a catalyst for synthesizing toluene diamine by hydrogenating dinitrotoluene, which has the advantages of simple preparation, low cost and long service life.
The preparation method of the invention comprises the following steps:
(1) carrying out dry grinding on the dried laterite-nickel ore to ensure that the granularity of the ore powder is less than or equal to 2mm, then adding 5-20wt% of additive into the crushed laterite-nickel ore, uniformly mixing, and placing in a reactor with stirring;
(2) heating and reducing the mineral powder in the reactor under the condition of reducing gas to ensure that non/weakly magnetic Fe in the mineral powder2O3NiO to magnetic Fe3O4Cooling Fe and Ni to normal temperature under the protection of nitrogen;
(3) carrying out wet fine grinding and size mixing on the ore powder subjected to reduction and magnetization in the step (2), then feeding the ore powder into a magnetic separator, carrying out magnetic separation in a magnetic field, and dehydrating the obtained magnetic minerals to obtain nickel concentrate;
(4) and reducing and activating the obtained nickel concentrate to obtain the hydrogenation catalyst.
As mentioned above in step (1), the lateritic nickel ore has an initial nickel content of 1.00-1.35 wt% and an initial iron content of 28.0-33.5 wt%.
As mentioned above, in the step (1), the laterite-nickel ore drying conditions are as follows: drying at the temperature of 110 ℃ for 6-8 h.
As mentioned above, in step (1), the additive is Na2CO3Or CaO;
in the step (2), the reduction temperature of the ore powder is 750-.
The reducing gas introduced in the step (2) is producer gas, coke oven gas or other H-rich gas2And CO.
In step (3), the magnetic separation condition is a magnetic field strength of 0.1-0.2T.
In the step (4), the reduction condition is 500-600 ℃, the reduction activation is 3-6h, and the space velocity of the reducing gas is 8-12L/(g.h).
In step (4) as described above, the reducing gas is H2And N2Mixed gas of (wherein H)2/N2The molar ratio is 1:3-1: 5).
The hydrogenation catalyst is applied to the synthesis of toluene di-tert-butyl by hydrogenation of dinitrotolueneAmmonia is particularly suitable for the hydrogenation reaction of synthesizing toluene diamine by hydrogenating dinitrotoluene in a slurry bed (batch), and the reaction conditions are controlled as follows: the reaction temperature is 110-2Stamping, continuously introducing hydrogen in the reaction process to maintain the pressure constant), wherein the reaction medium is methanol, and the concentration of the catalyst is 0.8-1.2 wt%.
The invention discloses a method for preparing and synthesizing a hydrogenation catalyst by utilizing laterite-nickel ore, which has the substantial characteristics and the progress compared with the traditional catalyst preparation method that:
1) the catalyst carrier and the active components of the invention are both from laterite nickel ore, no additional active component and catalytic assistant are needed, the cost of the catalyst is greatly reduced, and the batch production of the hydrogenation catalyst is easy to realize.
2) The catalyst is rich in active metals Ni and Fe, the hydrogenation catalyst after reduction activation is a Ni-Fe alloy type catalyst, and due to the existence of the synergistic action between Ni and Fe, the catalytic activity of the catalyst is higher than that of a catalyst which is singly loaded with iron or nickel under the same loading capacity.
3) According to the invention, high-temperature roasting reduction is carried out in the laterite-nickel ore treatment process, so that the finally prepared catalyst has higher chemical stability and thermal stability, and the sintering resistance of the catalyst is improved.
Detailed Description
The following examples are provided to further illustrate the technical means and effects of the present invention for achieving the intended purpose, but the present invention is not limited by the following examples.
Example 1
Drying a laterite-nickel ore sample with the initial Ni content of 1.10 wt% and the Fe content of 28.1 wt% at 100 ℃ for 8h, crushing the laterite-nickel ore sample to be less than or equal to 2mm, and adding 15 wt% of Na2CO3Placing the mixture in a reactor with stirring, heating to 800 ℃, and introducing the producer gas (CH) with the space velocity of 140L/(g.h)40.7vol％，H212.4vol％，CO 27.3vol％，CO26.2 vol%, and the other 53.4 vol%) for 200min, cooling to normal temperature under the protection of nitrogen, magnetically separating the obtained magnetized ore sample under the condition of magnetic field intensity of 0.15T to obtain nickel ore concentrate, and then carrying out magnetic separation on the nickel ore concentrateReducing gas (H) at 550 ℃ and a space velocity of 8L/(g.h)2/N2Reducing for 6 hours in a molar ratio of 1:4) to obtain a catalyst containing 4.6 wt% of nickel, 44.0 wt% of iron and 51.4 wt% of other carrier components such as silicon and aluminum. The conditions and results for evaluating the activity of the catalyst in the hydrogenation of dinitrotoluene are shown in Table 1.
The hydrogenation reaction comprises the following operation steps: 5g of the raw material (dinitrotoluene), 100ml of methanol and 0.9g of the catalyst were placed in a 250ml beaker and then poured into a slurry bed reactor (250 ml). The reaction vessel was replaced with hydrogen and nitrogen three times at room temperature, respectively, and after completion of the replacement, hydrogen was charged to a prescribed pressure to check the gas tightness. The airtightness is good, the temperature is increased to the specified temperature at the heating rate of 10 ℃/min, the reaction is carried out under the stirring condition of 500r/min, and hydrogen is continuously introduced in the reaction process to maintain the pressure to be constant.
Example 2
Drying a laterite-nickel ore sample with the initial Ni content of 1.28 wt% and the Fe content of 30.8 wt% at 100 ℃ for 8h, crushing the laterite-nickel ore sample to be less than or equal to 2mm, and adding 10 wt% of Na2CO3Placing the mixture in a reactor with stirring, heating the mixture to 900 ℃, and introducing producer gas (CH) with the space velocity of 180L/(g.h)40.7vol％，H212.4vol％，CO 27.3vol％，CO26.2 vol%, and the other 53.4 vol%) for reducing and magnetizing for 100min, cooling to normal temperature under the protection of nitrogen, magnetically separating the obtained magnetized ore sample under the condition of magnetic field intensity of 0.2T to obtain nickel concentrate, and reducing gas (H) with airspeed of 10L/(g.h) at 500 DEG C2/N2Reducing for 3 hours in a molar ratio of 1:3) to obtain a catalyst containing 5.8 wt% of nickel, 52.1 wt% of iron and 42.1 wt% of other carrier components such as silicon and aluminum.
The catalyst after reduction is used in the hydrogenation reaction of dinitrotoluene, the specific operation steps are the same as example 1, and the specific reaction conditions and results are shown in the attached table 1.
Example 3
Drying a laterite-nickel ore sample with the initial Ni content of 1.32 wt% and the Fe content of 33.5 wt% at 105 ℃ for 6h, crushing the laterite-nickel ore sample to be less than or equal to 2mm, and adding 20wt% of Na2CO3Placing the mixture in a reactor with stirring, raising the temperature to 1000 ℃, and introducing coke oven gas (g h) with space velocity of 120L/(g h)CH425.3vol％，H260.5vol％，CO 6.2vol％，C2+Unsaturated hydrocarbon 3.0 vol%, CO22.0vol％，O20.5 vol%, and other 2.5 vol%) for 240min, cooling to normal temperature under nitrogen protection, magnetically separating the obtained magnetized sample at magnetic field strength of 0.1T to obtain nickel concentrate, and reducing gas (H) at 600 deg.C and space velocity of 12L/(g H)2/N2Reducing for 4 hours in a molar ratio of 1:5) to obtain a catalyst containing 5.1 wt% of nickel, 49.6 wt% of iron and 45.3 wt% of other carrier components such as silicon and aluminum.
The catalyst after reduction is used in the hydrogenation reaction of dinitrotoluene, the specific operation steps are the same as example 1, and the specific reaction conditions and results are shown in the attached table 1.
Example 4
Drying a laterite-nickel ore sample with the initial Ni content of 1.03 wt% and the Fe content of 29.5 wt% at 105 ℃ for 7h, crushing the laterite-nickel ore sample to be less than or equal to 2mm, adding 5 wt% of CaO, placing the crushed laterite-nickel ore sample into a reactor with stirring, heating the crushed laterite-nickel ore sample to 900 ℃, and introducing generator gas (CH) with the space velocity of 140L/(g h)425.3vol％，H260.5vol％，CO 6.2vol％，C2+Unsaturated hydrocarbon 3.0 vol%, CO22.0vol％，O20.5 vol%, and other 2.5 vol%) for 60min, cooling to normal temperature under nitrogen protection, magnetically separating the obtained magnetized sample at magnetic field strength of 0.15T to obtain nickel concentrate, and reducing gas (H) at 600 deg.C and space velocity of 12L/(g H)2/N2Reducing for 3 hours in a molar ratio of 1:4) to obtain a catalyst containing 4.8 wt% of nickel, 43 wt% of iron and 52.2 wt% of other carrier components including silicon, aluminum and the like.
The catalyst after reduction is used in the hydrogenation reaction of dinitrotoluene, the specific operation steps are the same as example 1, and the specific reaction conditions and results are shown in the attached table 1.
Example 5
Drying a laterite-nickel ore sample with the initial Ni content of 1.20 wt% and the Fe content of 32.1 wt% at 110 ℃ for 6H, crushing the laterite-nickel ore sample to be less than or equal to 2mm, adding 15 wt% of CaO, placing the crushed laterite-nickel ore sample into a reactor with stirring, heating the reactor to 1000 ℃, and introducing water gas (H) with the space velocity of 120L/(g H)250vol％，CO 40vol％，CO29 vol%, other 1 vol%) reduction magnetization for 90min, and then keeping in nitrogenCooling to normal temperature, magnetically separating the obtained magnetized mineral sample at magnetic field strength of 0.2T to obtain nickel concentrate, and reducing gas (H) at 550 deg.C and space velocity of 10L/(g H)2/N2Reducing for 5 hours in a molar ratio of 1:5) to obtain a catalyst containing 4.8 wt% of nickel, 43 wt% of iron and 52.2 wt% of other carrier components including silicon, aluminum and the like.
The catalyst after reduction is used in the hydrogenation reaction of dinitrotoluene, the specific operation steps are the same as example 1, and the specific reaction conditions and results are shown in the attached table 1.
Attached table 1
Claims (10)
1. A preparation method of a catalyst for synthesizing toluenediamine by hydrogenating dinitrotoluene is characterized by comprising the following steps: the preparation method of the invention comprises the following steps:
(1) dry grinding the dried laterite-nickel ore to ensure that the granularity of the ore powder is less than or equal to 2mm, then adding 5-20wt% of additive into the crushed laterite-nickel ore, uniformly mixing, and placing in a reactor with stirring, wherein the additive is Na2CO3Or CaO;
(2) heating, reducing and magnetizing the mineral powder in the reactor under the condition of reducing gas, and then cooling to normal temperature under the protection of nitrogen, wherein the reduction temperature of the mineral powder is 750-240 ℃ and the reduction time is 60-240min, and the airspeed of the reducing gas is 120-180L/g.h;
(3) carrying out wet fine grinding and size mixing on the ore powder subjected to reduction and magnetization in the step (2), then feeding the ore powder into a magnetic separator, carrying out magnetic separation in a magnetic field, and dehydrating the obtained magnetic minerals to obtain nickel concentrate;
(4) and reducing and activating the obtained nickel concentrate to obtain the hydrogenation catalyst, wherein the reduction condition is 500-600 ℃, the reduction activation lasts for 3-6h, and the airspeed of the reducing gas is 8-12L/g.h.
2. The method for preparing the catalyst for the hydrogenation synthesis of toluenediamine from dinitrotoluene according to claim 1, characterized in that in the step (1), the laterite-nickel ore has an initial nickel content of 1.00-1.35 wt% and an initial iron content of 28.0-33.5 wt%.
3. The preparation method of catalyst for the hydrogenation synthesis of toluenediamine from dinitrotoluene according to claim 1, characterized in that in step (1), the drying conditions of lateritic nickel ore are as follows: drying at the temperature of 110 ℃ for 6-8 h.
4. The method according to claim 1, wherein the reducing gas introduced in step (2) is enriched in H2And CO.
5. The method of claim 4 wherein the catalyst is rich in H2And the gas of the CO is producer gas or coke oven gas.
6. The method for preparing catalyst for hydrogenation of dinitrotoluene to toluenediamine according to claim 1, wherein in step (3), said magnetic separation condition is magnetic field intensity of 0.1-0.2T.
7. The method according to claim 1, wherein the reducing gas in step (4) is H2And N2In which H is2/N2The molar ratio is 1:3-1: 5.
8. A catalyst prepared by the process of any one of claims 1 to 7, characterized in that it is prepared by the process of any one of claims 1 to 7.
9. The use of the catalyst of claim 8 wherein the hydrogenation catalyst is used in the hydrogenation of dinitrotoluene to form toluenediamine.
10. The use of the catalyst according to claim 9, wherein the hydrogenation catalyst is suitable for the hydrogenation of slurry bed dinitrotoluene to synthesize toluenediamine, and the reaction conditions are controlled as follows: the reaction temperature is 110 ℃ and 140 ℃, the reaction pressure is 1.0-3.0MPa, the reaction medium is methanol, and the concentration of the catalyst is 0.8-1.2 wt%.
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