CN114632539B - Catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol, and preparation method and application thereof - Google Patents
Catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol, and preparation method and application thereof Download PDFInfo
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- CN114632539B CN114632539B CN202011493724.6A CN202011493724A CN114632539B CN 114632539 B CN114632539 B CN 114632539B CN 202011493724 A CN202011493724 A CN 202011493724A CN 114632539 B CN114632539 B CN 114632539B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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Abstract
The application discloses a catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol, a preparation method and application thereof, wherein the catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol comprises a transition metal element M and a ZSM-5 molecular sieve; the transition metal element M is doped into the framework of the ZSM-5 molecular sieve; the transition metal element M is at least one selected from titanium, vanadium, manganese, iron, cobalt, nickel and copper. The catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol can be used for preparing acetonitrile by ammonification and dehydrogenation of ethanol, and can effectively improve the conversion rate of ethanol and the selectivity of acetonitrile, so that the catalyst has a good industrial application prospect.
Description
Technical Field
The application relates to an acetonitrile catalyst prepared by ammonification and dehydrogenation of ethanol, and a preparation method and application thereof, and belongs to the technical field of chemistry and chemical engineering.
Background
Acetonitrile is not only an excellent solvent, but also an important fine chemical organic intermediate, and has important application in the fields of pharmacy, pesticide, organic synthesis and petrochemical industry. The vast majority of acetonitrile in the world is extracted from byproducts of acrylonitrile production, the yield is only 1% -2% of the acrylonitrile yield, along with the continuous development of downstream product development technology of acetonitrile, the demand of acetonitrile is continuously increased, and the market has shown a tendency of undersupply. Therefore, development of a new technology for directly synthesizing acetonitrile has been eagerly made.
Acetonitrile can be synthesized by chemical methods such as carbon monoxide ammoxidation, lower hydrocarbon ammoxidation or reaction with cyano compounds, acetaldehyde oxime dehydration, acetaldehyde ammoxidation dehydration, ethanol ammoxidation dehydrogenation or oxidation, acetic acid ammoxidation dehydration, and the like. Compared with various acetonitrile synthesis processes, the ethanol direct ammoniation method has the advantages of simple process, low energy consumption, high atom utilization rate, high acetonitrile selectivity, low operation cost, no corrosion to equipment and the most industrial prospect. Development of an efficient ammonification dehydrogenation catalyst is a key for completing the technology of synthesizing acetonitrile by ammonification of ethanol. In the reaction process, the performance of the catalyst determines the conversion rate of ethanol and the yield of acetonitrile, and the traditional catalyst is mainly an active alumina-supported copper catalyst. However, activated alumina supported Cu-based catalysts are prone to deactivation, have poor stability and often require higher ammonia/alcohol ratios in the alcohol dehydrogenation ammonification reaction to achieve higher acetonitrile selectivity. The excessive ammonia-alcohol ratio aggravates the deactivation of the catalyst and increases the energy consumption of ammonia recycling. Therefore, the development of a high-efficiency novel catalyst solves the problems of poor catalyst stability and high ammonia-alcohol ratio in the reaction process faced by the existing catalyst system, and has very important significance in exploring the industrial application of the catalyst in synthesizing acetonitrile by ammonifying ethanol.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an acetonitrile catalyst prepared by ammonification and dehydrogenation of ethanol, and a preparation method and application thereof.
According to a first aspect of the present application, there is provided an ethanol ammonification and dehydrogenation process for preparing acetonitrile catalyst, the ethanol ammonification and dehydrogenation process for preparing acetonitrile catalyst comprising transition metal element M and ZSM-5 molecular sieve;
the transition metal element M is doped into the framework of the ZSM-5 molecular sieve;
the transition metal element M is at least one selected from titanium, vanadium, manganese, iron, cobalt, nickel and copper.
Optionally, the mass content of the transition metal element M in the catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol is 0.5-10%.
Alternatively, the upper limit of the mass content of the transition metal element M in the catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol is independently selected from 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, and the lower limit is independently selected from 0.5%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%.
According to a second aspect of the present application, there is provided a method for preparing an acetonitrile catalyst by ammonification and dehydrogenation of ethanol, the method comprising:
(1) Hydrothermally crystallizing a mixture containing a structure directing agent, water, a silicon source, an aluminum source, a hydroxide of an alkali metal ion M' and a transition metal element M source at 130-200 ℃ for 2-10 days;
(2) After crystallization is completed, washing, drying and roasting are sequentially carried out, and the acetonitrile catalyst prepared by ammonification and dehydrogenation of ethanol can be obtained;
in the mixture, the molar ratio of each substance is as follows:
SiO 2 ：Al 2 O 3 ：M’ 2 O：H 2 o: transition metal element M oxide: structure directing agent = 1:0.001-0.1:0.002-1:50:0.001-0.5:0.05-5.
Alternatively, the upper temperature limit of the hydrothermal crystallization is independently selected from 200 ℃, 190 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, and the lower temperature limit is independently selected from 130 ℃, 190 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃.
Alternatively, the hydrothermal crystallization may be independently selected from the group consisting of 10 days, 8 days, 6 days, 4 days, and 3 days for an upper limit and 2 days, 8 days, 6 days, 4 days, and 3 days for a lower limit.
Optionally, the silicon source is selected from one of ethyl orthosilicate, white carbon black, silica sol and sodium silicate;
the aluminum source is selected from one of aluminum sulfate, aluminum nitrate, sodium metaaluminate, aluminum isopropoxide and aluminum sol;
the hydroxide of the alkali metal ion M' is selected from sodium hydroxide;
the structure directing agent is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
Optionally, the method comprises: mixing raw materials required for preparing the transition metal doped ZSM-5 molecular sieve, a silicon source, an aluminum source, an alkali source, transition metal salt, a structure directing agent and water according to the mole ratio of oxides: 1SiO 2 ：0.001-0.1Al 2 O 3 :0.002-1Na 2 O:50H 2 O:0.001-0.5MO X 0.05-5SDA, and performing hydrothermal crystallization for 2-10 days at 130-200 ℃; washing, drying and roasting with deionized water after crystallization is completed, wherein SDA is a structure directing agent.
Alternatively, the source of the transition metal element M is selected from at least one of transition metal element M salts.
Optionally, the firing conditions are: the temperature is 300-600 ℃; the time is 3-10 h.
Optionally, the method further comprises the steps of:
(3) And in a hydrogen-containing atmosphere, reducing the roasted material to obtain the catalyst for preparing acetonitrile by ammonifying and dehydrogenating ethanol.
Optionally, the conditions of the reduction are: the temperature is 200-500 ℃; the time is 0.5-5 h.
According to a third aspect of the present application there is provided a process for preparing acetonitrile, the process comprising: reacting materials containing ethanol and ammonia in the presence of a catalyst to obtain acetonitrile;
the catalyst is selected from any one of the catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol and the catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol, which are prepared by the method.
Optionally, in the material, the molar ratio of ethanol to ammonia is 1:1.5 to 5.
Alternatively, the conditions of the reaction are: the temperature is 200-450 ℃; the pressure is 0.2-5.0Mpa; the mass space velocity of the ethanol is 0.2-2h -1 。
Alternatively, the upper limit of the reaction temperature is independently selected from 450 ℃, 400 ℃, 350 ℃, 300 ℃, 250 ℃, and the lower limit is independently selected from 200 ℃, 400 ℃, 350 ℃, 300 ℃, 250 ℃.
Alternatively, the upper limit of the reaction pressure is independently selected from 5Mpa, 4Mpa, 3Mpa, 2Mpa, 1Mpa, 0.5Mpa, and the lower limit is independently selected from 0.2Mpa, 4Mpa, 3Mpa, 2Mpa, 1Mpa, 0.5Mpa.
The catalyst is used for preparing acetonitrile by ammonification and dehydrogenation of ethanol, and the specific reaction process is as follows: the catalyst is filled in a fixed bed reactor and H is used before the reaction 2 And N 2 Reducing the mixed gas; then the raw material ethanol and ammonia gas are respectively introduced into a fixed bed reactor for reaction, and the mol ratio of ethanol to ammonia is 1/1.5-5; the reaction temperature is 200-450 ℃; the pressure of the reactor is 0.2-5.0Mpa; the mass space velocity of the ethanol is 0.2-2h -1 . The acetonitrile catalyst prepared by ammonification and dehydrogenation of ethanol is a transition metal doped ZSM-5 molecular sieve.
Alternatively, the transition metal element M in the catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol in the application can exist in an oxide form or in a simple substance form, and if the catalyst is prepared without a reduction process, the reduction can be performed in the process of preparing acetonitrile.
The beneficial effects that this application can produce include:
the catalyst is used for the reaction of preparing acetonitrile by ammonification and dehydrogenation of ethanol, and effectively improves the conversion rate of ethanol and the selectivity of acetonitrile, so that the catalyst has a good industrial application prospect.
Detailed Description
The present invention will be further described with reference to specific examples, but it should be noted that the present invention is not limited thereto.
Example 1
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker for stirring, then slowly dripping 20.83g of tetraethoxysilane into the beaker, and stirring uniformly at room temperature; 0.75g of aluminum nitrate, 0.2g of nickel nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the solution is added into the solution after being stirred uniformly at room temperature, and the solution is continuously stirred until uniform. Then pouring the synthetic solution into a polytetrafluoroethylene liner, sealing the liner in a stainless steel kettle, and crystallizing the liner for 2 days at 180 ℃. Quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for a plurality of times, drying, and roasting at 300 ℃ for 10 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: siO (SiO) 2 :0.01Al 2 O 3 :0.05Na 2 O:50H 2 O:0.01NiO 2 :0.25SDA。
Example 2
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker for stirring, then slowly dripping 20.83g of tetraethoxysilane into the beaker, and stirring uniformly at room temperature; 0.75g of aluminum nitrate, 0.5g of copper nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the solution is added into the solution after being stirred uniformly at room temperature, and the solution is continuously stirred until uniform. Then pouring the synthetic solution into a polytetrafluoroethylene liner, sealing the liner in a stainless steel kettle, and crystallizing the liner for 2 days at 180 ℃. Quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for a plurality of times, drying, and roasting at 400 ℃ for 8 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: siO (SiO) 2 :0.01Al 2 O 3 :0.05Na 2 O:50H 2 O:0.01CuO:0.25SDA。
Example 3
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker for stirring, then slowly dripping 20.83g of tetraethoxysilane into the beaker, and stirring uniformly at room temperature; 0.75g of aluminum nitrate, 0.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the solution is added into the solution after being stirred uniformly at room temperature, and the solution is continuously stirred until uniform. Then pouring the synthetic solution into a polytetrafluoroethylene liner, sealing the liner in a stainless steel kettle, and crystallizing the liner for 2 days at 180 ℃. Quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for a plurality of times, drying, and roasting at 500 ℃ for 7 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: siO (SiO) 2 :0.01Al 2 O 3 :0.05Na 2 O:50H 2 O:0.01CoO:0.25SDA。
Example 4
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker for stirring, then slowly dripping 20.83g of tetraethoxysilane into the beaker, and stirring uniformly at room temperature; 0.75g of aluminum nitrate, 0.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the solution is added into the solution after being stirred uniformly at room temperature, and the solution is continuously stirred until uniform. Then pouring the synthetic solution into a polytetrafluoroethylene liner, sealing the liner in a stainless steel kettle, and crystallizing the liner for 2 days at 180 ℃. Quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for a plurality of times, drying, and roasting at 600 ℃ for 6 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: siO (SiO) 2 :0.033Al 2 O 3 :0.05Na 2 O:50H 2 O:0.01CoO:0.25SDA。
Example 5
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker for stirring, then slowly dripping 20.83g of tetraethoxysilane into the beaker, and stirring uniformly at room temperature; 0.75g of aluminum nitrate, 2.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the solution is added into the solution after being stirred uniformly at room temperature, and the solution is continuously stirred until uniform. Then the synthetic solution is addedPouring into polytetrafluoroethylene liner, sealing in stainless steel kettle, crystallizing at 180deg.C for 2 days. Quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for a plurality of times, drying, and roasting at 450 ℃ for 7.5 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: siO (SiO) 2 :0.033Al 2 O 3 :0.05Na 2 O:50H 2 O:0.02CoO:0.25SDA。
Example 6
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker for stirring, then slowly dripping 20.83g of tetraethoxysilane into the beaker, and stirring uniformly at room temperature; 0.75g of aluminum nitrate, 2.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the solution is added into the solution after being stirred uniformly at room temperature, and the solution is continuously stirred until uniform. Then pouring the synthetic solution into a polytetrafluoroethylene liner, sealing the liner in a stainless steel kettle, and crystallizing the liner for 2 days at 200 ℃. Quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for a plurality of times, drying, and roasting at 500 ℃ for 7 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: siO (SiO) 2 :0.033Al 2 O 3 :0.05Na 2 O:50H 2 O:0.05CoO:0.25SDA。
Comparative example 1
9g of copper nitrate is added into 50mL of water, heated to 60 ℃ and stirred until the copper nitrate is completely dissolved, and a mixed solution is obtained; adding 10g of alumina microspheres into the prepared copper nitrate mixed solution by adopting an impregnation method, and excessively impregnating for 4 hours under the water bath condition of 60 ℃; the alumina microsphere after being immersed in the catalyst is dried for 12 hours at room temperature, then dried for 24 hours at 110 ℃, and then baked for 8 hours at 550 ℃ to obtain the catalyst.
Example 7
The catalysts prepared in examples 1-6 and comparative example 1 above were used in the ammonification and dehydrogenation of ethanol to acetonitrile. The specific implementation process is as follows: tabletting the catalyst, crushing the catalyst into particles with 20-40 meshes, weighing 1g of catalyst particles, and placing the particles in a fixed bed reactor, wherein the inner diameter of the fixed bed reactor is 10mm, and both ends of the fixed bed reactor are filled with quartz sand; the catalyst was pre-reacted with H at a flow rate of 50mL/min 2 Sum streamReducing the mixed gas consisting of 100mL/min of nitrogen at 400 ℃ for 2 hours, and then adding ethanol at a mass space velocity of 1 hour -1 Is pumped into the reactor in advance, and the flow rate of the ammonia gas is 200mL/min. The ethanol and ammonia gas are introduced into a fixed bed reactor for catalytic reaction to obtain a reaction product, and the reaction product is analyzed by adopting Agilent 7890A gas chromatography, and the result is shown in the table 1 below.
Ethanol conversion = amount of ethanol converted by reaction (mol)/ethanol feed (mol) ×100%
Acetonitrile selectivity = amount of ethanol converted to acetonitrile in reaction (mol)/amount of ethanol converted in reaction (mol) ×100%.
Table 1 properties of the catalysts prepared in examples 1 to 6 and comparative example 1.
| Catalyst | Ethanol conversion | Acetonitrile selectivity |
| Example 1 | 92.8％ | 96.0％ |
| Example 2 | 96.1％ | 95.8％ |
| Example 3 | 95.2％ | 97.1％ |
| Example 4 | 93.4％ | 98.0％ |
| Example 5 | 93.6％ | 97.5％ |
| Example 6 | 94.1％ | 97.8％ |
| Comparative example 1 | 70.5％ | 85.6％ |
As can be seen from Table 1, the catalysts prepared in examples 1 to 6 of the present invention have a conversion rate of ethanol of 90% or more and a selectivity of acetonitrile of 95% or more, indicating excellent catalytic activity. Comparing comparative example 1 with the examples, it is known that the transition metal doped ZSM-5 molecular sieve has excellent catalytic performance, and the excellent performance mainly comes from the strong acidic center of the ZSM-5 molecular sieve and the transition metal active center with the surface highly evenly distributed.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A method for preparing acetonitrile is characterized in that materials containing ethanol and ammonia gas react in the presence of a catalyst to obtain acetonitrile;
the catalyst comprises a transition metal element M and a ZSM-5 molecular sieve;
the transition metal element M is doped into the framework of the ZSM-5 molecular sieve;
the transition metal element M is at least one selected from titanium, vanadium, manganese, iron, cobalt, nickel and copper.
2. The method according to claim 1, wherein the mass content of the transition metal element M in the catalyst is 0.5 to 10%.
3. The method according to claim 1, wherein the method for preparing the catalyst comprises:
(1) Hydrothermally crystallizing a mixture containing a structure directing agent, water, a silicon source, an aluminum source, a hydroxide of an alkali metal ion M' and a transition metal element M source at 130-200 ℃ for 2-10 days;
(2) After crystallization is completed, washing, drying and roasting are sequentially carried out to obtain the catalyst;
in the mixture, the molar ratio of each substance is as follows:
SiO 2 ：Al 2 O 3 ：M’ 2 O：H 2 o: transition metal element M oxide: structure directing agent = 1:0.001-0.1:0.002-1:50:0.001-0.5:0.05-5.
4. A method according to claim 3, wherein the silicon source is selected from one of ethyl orthosilicate, white carbon black, silica sol, sodium silicate;
the aluminum source is selected from one of aluminum sulfate, aluminum nitrate, sodium metaaluminate, aluminum isopropoxide and aluminum sol;
the hydroxide of the alkali metal ion M' is selected from sodium hydroxide;
the structure directing agent is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
5. A method according to claim 3, wherein the source of transition metal element M is selected from at least one of the salts of transition metal element M.
6. A method according to claim 3, wherein the firing conditions are: the temperature is 300-600 ℃; the time is 3-10 h.
7. A method according to claim 3, wherein the method of preparing the catalyst further comprises the steps of:
(3) And reducing the material obtained after roasting in a hydrogen-containing atmosphere to obtain the catalyst.
8. The method of claim 7, wherein the conditions for the reduction are: the temperature is 200-500 ℃; the time is 0.5-5 h.
9. The method according to claim 1, wherein the molar ratio of ethanol to ammonia in the feed is 1:1.5 to 5.
10. The method of claim 1, wherein the reaction conditions are: the temperature is 200-450 ℃; the pressure is 0.2-5.0Mpa; the mass space velocity of the ethanol is 0.2-2h -1 。
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