CN111215075B - Catalyst for coupling elimination of nitrous oxide in preparation of ethylene through oxidative dehydrogenation of ethane and preparation and application thereof - Google Patents
Catalyst for coupling elimination of nitrous oxide in preparation of ethylene through oxidative dehydrogenation of ethane and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for eliminating ethylene coupling nitrous oxide produced by oxidative dehydrogenation of ethane, and preparation and application thereof. In particular to a NiX composite metal oxide (NiX-MO) prepared by taking ultrathin NiX hydrotalcite (NiX-HT, X = Al, ga and In) as a precursor, wherein the active component is NiO, and the ratio of Ni to X can be regulated and controlled to be between 2 and 5. Wherein the ultra-thin NiX-HT is prepared by coprecipitation combined with microemulsion method, niX-MO is obtained by roasting hydrotalcite at temperature of400-700 ℃. The catalyst can be at 400-650 deg.C 2 H 6 And N 2 O volume ratio of 0.5-5, he or N 2 Under the equilibrium condition, ethane is converted into ethylene with high selectivity, and N can be eliminated 2 O, and does not deposit carbon, and does not deactivate after running for 240h continuously. The nickel-based catalyst improved based on the ultrathin hydrotalcite has the selectivity reaching 100 percent under a certain conversion rate. The important significance of ultrahigh ethylene selectivity lies in atom economy, ethane carbon atoms are nearly 100% utilized, and meanwhile, products are ethylene and water, so that the product separation cost is reduced, and the ultrahigh ethylene selectivity has a good industrial application prospect.
Description
Technical Field
The invention relates to a catalyst for eliminating ethylene coupling nitrous oxide produced by oxidative dehydrogenation of ethane, a preparation method and application thereof
Technical Field
Ethylene is an important organic chemical raw material and one of the important marks of the national petrochemical development level. Worldwide ethylene demand reached 1.53 million tons in 2016 and will also keep the demand rising at 520 million tons per year. At present, the raw materials for producing ethylene still mainly comprise naphtha and ethane. However, with the development of shale gas exploration and exploitation technology, the production rate of shale gas per year will reach 104% in 2012-2040 years (aust.j.agr.resource.eco.59 (2015) 571). The ethane is used as associated gas, the yield is increased greatly, and the cheap and sufficient raw materials enable the ethane to produce the ethylene with greater economic benefit. Taking the total cost of producing each ton of ethylene from different feedstocks in 2012 as an example (petrochemical technology and economics 1 (2015) 1), ethane is $ 521, imported ethane is $ 690, and naphtha is $ 1086. Since the production cost of ethane as a raw material is the lowest as compared with other raw materials, the proportion of ethane in the ethylene production raw material has been increasing in recent years.
The conventional mode of ethylene generation is dominated by steam cracking. But the steam cracking is limited by thermodynamics, the reaction temperature is about 1000 ℃, and the energy consumption is high; the number of byproducts is large, and the separation cost is high; the equipment is seriously coked and needs to be stopped and cleaned regularly. The ethylene preparation by oxidative dehydrogenation of ethane is an exothermic reaction, and thermodynamic limitation does not exist; the reaction temperature is lower (300-650 ℃), and the requirement on equipment is low; and the catalyst has no carbon deposition and equipment coking phenomena, and is a very promising ethylene production mode.
At present, the catalyst for preparing ethylene by oxidative dehydrogenation of ethane mainly comprises Pt-based, ni-based, mo-based composite oxides, alkali metal halides, carbon and boron nitride non-oxide catalysts. PtSn/Al is reported in literature (Science 285 (1999) 712) 2 O 3 Adding a large amount of hydrogen (C) into the reaction 2 H 6 :O 2 :H 2 = 2), ethane conversion was 73% at 950 ℃, and ethylene selectivity reached 83%. However, the reaction temperature is high, and the oxidation system is added with a large amount of hydrogen, so that the explosion risk is caused, and meanwhile, the cost of the noble metal is high, and the large-scale application is difficult. United carbon patents (US Patent 4250346 and CN 85 1 03650A) reported that the movnbscao catalyst had an ethane conversion of 73% and an ethylene selectivity of 71% at 400 ℃, and conducted a pilot plant. However, the catalyst and the preparation conditions are relatively complex, so that the catalyst repeatability is to be improved, and the industrialization is not realized at present. LiKCl/MgO + Dy reported in the literature (J.Am.chem.Soc.136 (2014) 12691) 2 O 3 At 625 ℃, the ethane conversion rate of the catalyst reaches 80%, the ethylene selectivity reaches 90%, but after a period of reaction, the catalyst is obviously deactivated due to Cl loss. The literature (ACS Catal.6 (2016) 2852) reports that the NiMO (M = Sn, ti, W) catalyst has ethane conversion rate of 30% and ethylene selectivity of 80% under the condition of 350 ℃, and the NiO-based catalyst has better reaction activity but is easily over-oxidized to reduce the selectivity. The ethylene selectivity of the catalyst is best about 90 percent at present, and the catalyst shows the reaction performance close to 100 percent selectivity.
In the system of ethane oxidative dehydrogenation coupled with nitrous oxide elimination, the common catalyst comprises a supported Fe-based, V-based and Mo-based catalyst. The Fe-ZSM5 catalyst reported in the literature (appl. Catal. B-environ.64 (2006) 201) has the ethane conversion rate of 22% and the ethylene selectivity of 70% under the condition of 400 ℃, but aromatic organic matters are easily generated on the Fe-based catalyst to cause the catalyst deactivation. The Mo/Si-Ti catalyst reported in the literature (J.Phy.chem.C 113 (2009) 10112) has ethane conversion of 4.3% and ethylene selectivity of 85% at 600 ℃. Although these catalysts show superior selectivity under nitrous oxide conditions compared to oxygen systems, overall ethylene selectivity is not high. Therefore, it is of great significance to develop a catalyst which can eliminate nitrous oxide and generate ethylene with high selectivity.
Disclosure of Invention
The invention provides a catalyst for eliminating ethylene coupling nitrous oxide produced by oxidative dehydrogenation of ethane and a preparation method and application thereof. Elimination as referred to herein means facilitating dissociation of nitrogen-oxygen bonds, promoting N 2 And (4) decomposing the O.
In order to achieve the purpose, the technical scheme of the invention is as follows: the catalyst for eliminating ethylene coupled nitrous oxide produced by oxidative dehydrogenation of ethane is a composite oxide consisting of Ni and an auxiliary agent X, and is expressed as NiX-MO, and the molar ratio of Ni to X is 2-5.
Taking the NiAl-MO catalyst as an example, the preparation method comprises the following steps: mixing Ni (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in water according to the required molar ratio to obtain the metal salt solution. Then NaOH and alkali metal salt are dissolved in water together to obtain alkali metal salt solution. Putting an alkali metal salt solution in a water bath at 20-90 ℃, dripping the metal solution into the alkali solution at 1-3mL/min, continuously stirring, adding Sodium Dodecyl Sulfate (SDS), adjusting the pH to 9.0-12.0 by using 1-4M NaOH, continuously stirring for 12-24 h, filtering, washing, drying, and calcining in a muffle furnace at 400-700 ℃ for more than 1h to obtain the NiAl-MO catalyst.
The reaction condition for eliminating the ethylene coupling nitrous oxide prepared by the oxidative dehydrogenation of ethane is continuous fixed bed reaction, and raw material gas forms C 2 H 6 Pressure 2-50kPa, C 2 H 6 And N 2 O volume ratio of 0.5-5, he or N 2 Under the condition of equilibrium and normal pressure, the space velocity is 6000 to 72000mL/g cat /h。
Compared with the prior art, the invention has the substantial characteristics that:
1. according to the invention, the thickness of the hydrotalcite can be regulated and controlled by using the amount of SDS (sodium dodecyl sulfate) as a surfactant by using a coprecipitation combined microemulsion method, so that an ultrathin hydrotalcite precursor is obtained, and the NiX-MO catalyst is obtained after roasting, has a stable structure and does not deactivate after continuously running for 240 hours.
2. The invention can convert ethane into ethylene with high selectivity, and when the ethane conversion rate is 10%, the selectivity of ethylene is close to 100%. At 27% conversion, ethylene selectivity was greater than 90%, which is the best result in nickel oxide based catalysts.
3. The invention can utilize N at the same time 2 O is an oxidant and can be used for greenhouse gas N 2 The conversion of O is eliminated.
Drawings
Fig. 1 is an XRD pattern of hydrotalcite precursor obtained by adding different contents of surfactant.
FIG. 2 is a TEM image of hydrotalcite precursors obtained by adding different amounts of surfactant, wherein (a) SDS is 0g, (b) SDS is 0.9g, (c) SDS is 3.6g, (d) SDS is 14.4g.
FIG. 3 shows Ni 3 Catalytic performance of Al-MO at different temperatures.
FIG. 4 shows Ni 3 The catalytic performance of the Al-MO at different space velocities is compared with the results of the prior literature.
FIG. 5 shows the formula of Ni 3 Evaluation of stabilizer for Al-MO.
Detailed Description
The following examples will help to understand the present invention, but the scope of the present invention is not limited to these examples.
The present invention will be described in detail with reference to examples.
Example 1: ni 2 Al-MO catalyst preparation
9.70g of Ni (NO) 3 ) 2 ·6H 2 O and 6.25g of Al (NO) 3 ) 3 ·9H 2 O was dissolved together in 50mL of ultrapure water, and 2.40g of NaOH and 4.24g of Na were added 2 CO 3 The solutions were dissolved together in 50mL of ultrapure water. Putting the alkali solution into a water bath at 65 ℃, dropping the metal solution into the alkali solution at 2mL/min, continuously stirring, adding 14.4g of sodium dodecyl sulfate surfactant, adjusting the pH to 10.0 by NaOH, stirring in the water bath for 18h, filtering, washing and drying to obtain the ultrathin Ni 2 Al-HT hydrotalcite precursor (the number of layers of hydrotalcite is 1-10, the total thickness is 1-10 nm), and calcining in a muffle furnace at 600 ℃ for 3h to obtain the final productTo Ni 2 Al-MO catalyst.
Example 2: ni 3 Al-MO catalyst preparation
10.89g of Ni (NO) 3 ) 2 ·6H 2 O and 4.68g of Al (NO) 3 ) 3 ·9H 2 O was dissolved together in 50mL of ultrapure water, and 2.40g of NaOH and 4.24g of Na were added 2 CO 3 The solutions were dissolved together in 50mL of ultrapure water. Putting the alkali solution into a water bath at 65 ℃, dripping the metal solution into the alkali solution at 2mL/min, continuously stirring, adding 14.4g of sodium dodecyl sulfate surfactant, adjusting the pH to 10.0 by NaOH, stirring in the water bath for 18h, filtering, washing and drying to obtain the ultrathin Ni 3 Al-HT precursor (the number of layers of hydrotalcite is 1-10, the total thickness is 1-10 nm), and then calcining in a muffle furnace at 600 ℃ for 3h to obtain Ni 3 Al-MO catalyst.
Example 3: ni 4 Al-MO catalyst preparation
11.63g of Ni (NO) 3 ) 2 ·6H 2 O and 3.75g of Al (NO) 3 ) 3 ·9H 2 O was dissolved together in 50mL of ultrapure water, and 2.40g of NaOH and 4.24g of Na were added 2 CO 3 The solutions were dissolved together in 50mL of ultrapure water. Putting the alkali solution into a water bath at 65 ℃, dropping the metal solution into the alkali solution at 2mL/min, continuously stirring, adding 14.4g of sodium dodecyl sulfate surfactant, adjusting the pH to 10.0 by NaOH, stirring in the water bath for 18h, filtering, washing and drying to obtain the ultrathin Ni 4 Al-HT precursor (the number of layers of hydrotalcite is 1-10, the total thickness is 1-10 nm), and then calcining in a muffle furnace at 600 ℃ for 3h to obtain Ni 4 Al-MO catalyst.
Example 4: ni 3 Preparation of Ga-MO catalyst
10.89g of Ni (NO) 3 ) 2 ·6H 2 O and 5.22g of Ga (NO) 3 ) 3 ·9H 2 O was dissolved together in 50mL of ultrapure water, and 2.40g of NaOH and 4.24g of Na were added 2 CO 3 The solutions were dissolved together in 50mL of ultrapure water. Putting the aqueous alkali into a water bath at 65 ℃, dripping the metal solution into the aqueous alkali at 2mL/min, continuously stirring, adding 14.4g of sodium dodecyl sulfate surfactantAdjusting pH to 10.0 with NaOH, stirring in water bath for 18 hr, filtering, washing, and drying to obtain ultrathin Ni 3 Al-HT precursor (the number of layers of hydrotalcite is 1-10, the total thickness is 1-10 nm), and then calcining in a muffle furnace at 600 ℃ for 3h to obtain Ni 3 Ga-MO catalyst.
Example 5: ni 3 In-MO catalyst preparation
10.89g of Ni (NO) 3 ) 2 ·6H 2 O and 3.76g of In (NO) 3 ) 3 ·xH 2 O was dissolved together in 50mL of ultrapure water, and 2.40g of NaOH and 4.24g of Na were added 2 CO 3 The solutions were dissolved together in 50mL of ultrapure water. Putting the alkali solution into a water bath at 65 ℃, dripping the metal solution into the alkali solution at 2mL/min, continuously stirring, adding 14.4g of sodium dodecyl sulfate surfactant, adjusting the pH to 10.0 by NaOH, stirring in the water bath for 18h, filtering, washing and drying to obtain the ultrathin Ni 3 In-HT precursor (the number of layers of hydrotalcite is 1-10, the total thickness is 1-10 nm), and then calcining In a muffle furnace at 600 ℃ for 3h to obtain Ni 3 An In-MO catalyst.
Example 6: preparation of Ni by adjusting different amounts of SDS 3 Al-MO
10.89g of Ni (NO) 3 ) 2 ·6H 2 O and 4.68g of Al (NO) 3 ) 3 ·9H 2 O was dissolved together in 50mL of ultrapure water, and 2.40g of NaOH and 4.24g of Na were added 2 CO 3 The solutions were dissolved together in 50mL of ultrapure water. Putting the aqueous alkali into a water bath at 65 ℃, dripping the metal solution into the aqueous alkali at 2mL/min, continuously stirring, adding 14.4g,3.6g,0.9g and 0g of sodium dodecyl sulfate surfactant respectively, adjusting the pH to 10.0 by NaOH, stirring in the water bath for 18h, filtering, washing and drying to obtain the ultrathin Ni 3 Al-HT precursor (the number of layers of hydrotalcite is 1-10, the total thickness is 1-10 nm), and then calcining in a muffle furnace at 600 ℃ for 3h to obtain Ni 3 Al-MO catalyst.
Comparative example 1: niO/Al preparation by impregnation method 2 O 3 Catalyst and process for producing the same
3.15g of Ni (NO) were weighed 3 ) 2 ·6H 2 Dissolving O in proper amount of ultrapure water, adding 1g of gamma-Al 2 And O3, stirring uniformly, and soaking for 24 hours at room temperature. Then putting the mixture into an oven at 80 ℃ for overnight drying, uniformly grinding the mixture, and roasting the mixture in a muffle furnace at 600 ℃ for 3 hours to obtain NiO/Al 2 O 3 A catalyst.
Comparative example 2: preparation of cp-Ni by coprecipitation method 3 Al-MO catalyst
The specific preparation process is shown in example 6, when 0g of surfactant is added, the catalyst is prepared by coprecipitation method, and the obtained catalyst is named cp-Ni 3 Al-MO。
As a result, the
All ethane conversion and ethylene selectivity calculations in this patent are as follows:
C 2 H 6 conversion＝(C 2 H 6 (in)-C 2 H 6 (out))/C 2 H 6 (in)
C 2 H 4 selectivity＝C 2 H 4 (out)/(C 2 H 6 (in)-C 2 H 6 (out))
wherein C is 2 H 6 (in) represents the amount of ethane in the reaction gas; c 2 H 6 (out) represents the amount of ethane in the product; c 2 H 4 (out) represents the amount of ethylene in the product.
1. Different NiAl ratios and reaction properties of NiX catalysts
As shown in Table 1, it can be seen from examples 1,2,3 that Ni is obtained by adjusting different ratios of Ni and Al x The Al-MO catalyst shows excellent ethane oxidative dehydrogenation performance, and the selectivity of ethylene is more than 90%. Wherein Ni 3 The Al-MO catalyst has the highest activity, and the ethane conversion rate is 27% and the selectivity reaches 90% under the condition of 600 ℃. As can be seen from examples 4,5, ni was prepared 3 Ga-MO and Ni 3 The In-MO catalyst also shows better ethylene selectivity, and the selectivity is more than 90% under a certain conversion rate.
2. Reactivity of catalyst prepared by different preparation methods
Ni prepared by combining co-precipitation with microemulsion method in example 2 3 Al-MO catalyst, niO Al obtained by impregnation method in comparative example 1 2 O 3 Catalyst and cp-Ni co-precipitated in comparative example 2 3 Al-MO catalyst at different temperatures and normal pressure, C 2 H 6 :N 2 He =1 cat The evaluation was carried out under the conditions of/h, and the detailed results are shown in Table 2. NiO/Al obtained by impregnation 2 O 3 The catalyst has the lowest reaction temperature but the worst selectivity, and when the ethane conversion rate is close to 10 percent, the ethylene selectivity is only 55 percent; cp-Ni prepared by coprecipitation method 3 Al-MO, ethylene selectivity is improved to 73%; ni obtained by using ultra-thin hydrotalcite prepared by micro-emulsion method as precursor 3 Al-MO with selectivity higher than 98%.
3. Different amounts of SDS to Ni 3 Influence of Al-MO
Example 6 catalyst precursor Ni 3 The XRD results of Al-HT are shown in FIG. 1, and as the content of the surfactant increases, the intensity of the XRD peak decreases and the peak profile widens, indicating that the precursor becomes smaller. As a result of electron microscopy, as shown in fig. 2, it can be seen that the thickness of hydrotalcite gradually decreased. The detailed catalytic properties are shown in table 3. It can be seen that the selectivity of ethylene is improved from 61% to over 90% after the surfactant is added, which indicates that the selectivity of ethylene can be greatly improved by adding the surfactant. After the surfactant is added, the thickness of the hydrotalcite is gradually reduced, and the reaction activity of the catalyst is continuously improved correspondingly. Ni prepared from ultrathin hydrotalcite precursor at 600 DEG C 3 The Al-MO catalyst has ethane conversion rate of 27% and selectivity of 90%. 4.Ni 3 Catalytic performance of Al-MO under different oxidants
The catalyst obtained in example 2 was tested under the conditions of oxygen and nitrous oxide as oxidants, respectively. The results are shown in Table 1, example 2, at a reaction temperature of 600 ℃ and under normal pressure, C 2 H 6 :N 2 He =1 2 H 6 :O 2 He =2 (molar ratio) 1 cat Under the condition of h, with N 2 O is an oxidant, the conversion rate of ethane is 27%, and the selectivity reaches 90%; with O 2 The conversion of ethane was 50% and the selectivity reached 78% as oxidant. Description of O 2 Exhibits higher reactivity with N 2 O is the oxidant, and the selectivity is better.
5.Ni 3 Catalytic performance of Al-MO at different temperatures
The catalyst obtained in example 2 was subjected to 460 to 600 ℃ under normal pressure, respectively, to obtain C 2 H 6 :N 2 He =1 cat The results of the test under the/h condition are shown in FIG. 3. It can be seen that at low conversions the ethylene maintains 100% selectivity, at 560 ℃ the ethane conversion is 10% and the ethylene selectivity is greater than 98.3%, which is one of the best results reported so far.
6.Ni 3 Catalytic performance of Al-MO at different space velocities
The catalyst obtained in example 2 is used at a space velocity of 6000 to 72000mL/g cat At 600 ℃ under normal pressure, C 2 H 6 : N 2 He =1 (molar ratio) under 48 conditions. While comparing the results with the recent nickel-based catalysts under oxygen conditions. As shown in fig. 4, as the space velocity increases, ethane conversion decreases and ethylene selectivity increases. Ni prepared by thin-layer hydrotalcite in all nickel-based catalysts 3 The Al-MO catalyst has optimal ethylene selectivity.
7.Ni 3 Stability Properties of Al-MO
The catalyst obtained in example 2 was heated at 560 ℃ under normal pressure to obtain C 2 H 6 :N 2 He =1 cat The stability test was carried out for 240h under the/h conditions, the results are shown in FIG. 5. It can be seen that the activity of the catalyst is improved to a certain extent, the ethylene selectivity is reduced to a certain extent, but the ethylene selectivity is maintained to be more than 90%, and obvious inactivation does not occur after 240 hours of reaction.
TABLE 1 reactivity of different catalysts
TABLE 2 reactivity of catalysts prepared by different preparation methods
TABLE 3. Different surfactant amounts give Ni 3 Catalytic properties of Al-MO
Claims (4)
1. The application of the catalyst for eliminating the coupling nitrous oxide in the preparation of ethylene by oxidative dehydrogenation of ethane is characterized in that:
reacting in a fixed bed reactor filled with a catalyst, wherein the reaction is a continuous fixed bed reaction, and feeding a raw material gas C 2 H 6 Pressure 2-50kPa, in N 2 O and O 2 One or two of the raw materials are oxidant and raw material gas C 2 H 6 And oxidant in a volume ratio of 0.5-5, as He or N 2 One or two of the gases are balance gases, the total pressure of the gases introduced into the fixed bed reactor is normal pressure, and the total airspeed of the gases is 6000-72000mL g. cat -1 ·h -1 Passing through a fixed bed reactor filled with a catalyst;
the catalyst is a composite oxide consisting of Ni and an auxiliary agent X, and is expressed as NiX-MO;
the active component is NiO, and the auxiliary agent X is an oxide of Al; the atomic ratio of Ni and X is controlled between 2 and 5;
the catalyst is prepared by adopting a coprecipitation method combined with a microemulsion method, and the specific process is as follows:
1) Mixing Ni (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in water according to the required molar ratio to obtain a metal solution;
2) Dissolving NaOH and an alkali metal salt solution in water to obtain an alkali solution;
3) Putting an alkali solution in an environment of 20-90 ℃, dripping a metal solution into the alkali solution under the stirring condition, adding Sodium Dodecyl Sulfate (SDS), adjusting the pH to 9.0-12.0 by using 1-4M NaOH, then stirring for 12-24 h, filtering, washing and drying to obtain a hydrotalcite precursor NiAl-HT, and then calcining for more than 1h in a 400-700 ℃ muffle furnace to obtain a NiAl-MO catalyst;
the precursor before the catalyst is calcined is ultrathin hydrotalcite, the number of layers of the hydrotalcite is 1-10, and the total thickness is 1-10nm.
2. Use according to claim 1, characterized in that: ni (NO) in metal salt solution 3 ) 2 The molar concentration of (A) is 0.25-1.5M;
the molar concentration of NaOH in the alkali solution is 0.1-3M, and the molar concentration of alkali metal salt is 0.1-3M;
Ni(NO 3 ) 2 the molar ratio of the sodium hydroxide to NaOH in the alkali solution is 0.2-2;
the final molar concentration of the sodium dodecyl sulfate in the system is 0.01-1M.
3. Use according to claim 1, characterized in that: the selected alkali metal salt is one or more than two of sodium chloride, sodium carbonate, sodium sulfate, potassium chloride, potassium carbonate and potassium sulfate.
4. Use according to claim 3, characterized in that: the alkali metal salt is one or two of sodium carbonate and potassium carbonate.
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