CN113058586A - Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof - Google Patents
Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and a preparation method thereof, belonging to the technical field of catalysts. The invention aims to provide a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide. The catalyst takes CeZr solid solution as a carrier, Cr and an auxiliary agent are loaded on the carrier, the content of Cr is 8-15% and the content of the auxiliary agent is 0-10% based on 100% of the mass of the catalyst, and the molecular formula of the CeZr solid solution is CexZr1‑xO2X is 0.1-0.9, and the auxiliary agent is Li, Na, K, Mg,At least one of Ca and Sr. The catalyst of the invention adopts a specific cerium-zirconium solid solution as a carrier, and introduces an auxiliary agent, thereby obviously improving the selectivity and the carbon deposition resistance of the target product olefin. The catalyst has good carbon deposition resistance and obviously improved catalytic stability. And the preparation method is simple and has low cost and good industrial application prospect.
Description
Technical Field
The invention relates to a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and a preparation method thereof, belonging to the technical field of catalysts.
Background
With the development of the world economy, the demand for low-carbon olefins such as ethylene and propylene has been increasing, and particularly, ethylene is an important chemical raw material, which is a basic chemical raw material for synthetic fibers, synthetic rubbers, synthetic plastics (polyethylene and polyvinyl chloride), and synthetic ethanol (alcohol), and is also used for the production of vinyl chloride, styrene, ethylene oxide, acetic acid, acetaldehyde, explosives, and the like, and also as a ripener for fruits and vegetables. The preparation method of the light olefins is various, wherein, light hydrocarbon CO2Oxidative dehydrogenation (hereinafter abbreviated as CO)2-ODHE) is an important process, CO2The catalyst is used as an oxidant to participate in the reaction, not only can the conversion rate and the selectivity be improved, but also the CO can be fully utilized2By reducing CO2And (4) discharging.
For CO2The most abundant metal oxide catalysts for the-ODHE are Cr, V, Ga, In and Co, respectively. The Cr-based catalyst has multiple valence ions of Cr, and oxidation-reduction circulation is easily formed between high valence ions and low valence ions to CO2The ODHE has very good catalytic performance and is the most studied transition metal oxide catalyst at present. Cr-based catalysts tend to exhibit higher ethane conversion in a short time, but have a shorter lifetime due to their CO-to-CO ratio2The conversion rate is low, and the catalyst is easy to deposit carbon. The Cr oxide is loaded on SiO2When the catalyst is carried on carriers such as MCM-41, H-ZSM-5 and the like, the activity of the catalyst is greatly improved, and although Cr can be well dispersed in mesopores and can expose more active sites, more Cr exists in the form of low-activity polychromate. Increase Cr content6+/Cr3+The ratio of (A) to (B) is a main method for improving the activity of the Cr-based catalyst, and Li and the like realize the Cr-based catalyst Cr by introducing different additives6+/Cr3+Of a ratio ofRegulating and controlling, and further improving the activity of the catalyst. Since the V ion can be converted between trivalent, tetravalent, pentavalent, there is also much to be done with V-based catalysts. Research on V-based catalysts has focused more on the support on which they are supported, since the activity of vanadium oxides, like chromium, depends on the influence of the support on reducibility, acidity and basicity and dispersibility. V-based catalysts hold great promise for ODH reactions, but it remains a challenge to control the acidic sites that promote olefin cleavage, while there is some information about V2O5Dust health problems. Ga-based catalyst for activating CO by virtue of good adsorption2Ability to be applied to CO2-ODH. Unloaded Ga2O3Has better olefin selectivity, but the catalyst is quickly deactivated because of serious carbon deposition. And Ga after loading2O3Make alkane and CO2Competitive adsorption occurs, resulting in lower conversion of alkanes.
From this, the mainstream catalysts studied in many cases today have the following problems: the catalyst is affected by carbon deposition and is inactivated quickly. ② the Cr-based catalyst (such as the catofin process) applied in industry is regenerated frequently, and the 'reaction-purging-regeneration' single period is completed in about 30 min. ③ partial catalyst activates CO2The capacity is not strong, and the oxidation-reduction cycle is slowed down.
The invention patent with application number of 201910648815.3 discloses a metal supported catalyst, which comprises 80-99.9 parts of carrier and 0.1-20 parts of active component by weight of the catalyst; the active component comprises iron element and at least one element selected from cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum, and the carrier comprises cerium oxide and main group element oxide. The catalyst has good anti-carbon deposition capability, but is mainly used for low-carbon alkane and CO2Oxidative dehydrogenation produces synthesis gas (carbon monoxide and hydrogen are main components) and cannot be used for olefin production.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide.
The catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide takes CeZr solid solution as a carrier, Cr and an auxiliary agent are loaded on the carrier, the content of Cr is 8-15% and the content of the auxiliary agent is less than 10% based on 100% of the mass of the catalyst, and the molecular formula of the CeZr solid solution is CexZr1-xO2X is 0.1-0.9, and the auxiliary agent is at least one of Li, Na, K, Mg, Ca and Sr.
In one embodiment of the invention, the content of Cr is 9-11%, and the content of the auxiliary agent is 0.6-10%. In one embodiment of the invention, the content of Cr is 10% and the content of the auxiliary agent is 5%.
In some embodiments of the invention, the lower alkane is ethane, propane or butane.
In one embodiment of the present invention, x is 0.3 to 0.7. In one embodiment of the invention, x is 0.7.
In one embodiment of the present invention, the carrier is prepared by a uniform precipitation method, and the Cr and the auxiliary are supported on the carrier by an incipient wetness impregnation method.
The second technical problem to be solved by the invention is to provide the preparation method of the catalyst for preparing the olefin by oxidizing the low-carbon alkane with the carbon dioxide.
The invention relates to a preparation method of a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide, which comprises the following steps:
a. preparation of CeZr solid solution: uniformly mixing cerium salt, zirconium salt, urea and water, carrying out reflux reaction for 20-30 h, carrying out solid-liquid separation, washing and drying a precipitate, and then roasting at 400-600 ℃ to obtain a CeZr solid solution;
b. mixing chromium salt, auxiliary agent salt and water to form an impregnation solution, placing a CeZr solid solution in the impregnation solution for impregnation, then removing, drying, and roasting at 500-700 ℃ to obtain a catalyst; the auxiliary salt is at least one of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt and strontium salt.
In a specific embodiment of the present invention, the cerium salt is cerium nitrate, the zirconium salt is zirconium nitrate, the chromium salt is chromium nitrate, the lithium salt is lithium nitrate, the sodium salt is sodium nitrate, the potassium salt is potassium nitrate, the magnesium salt is magnesium nitrate, the calcium salt is calcium nitrate, and the strontium salt is strontium nitrate.
In one embodiment of the present invention, in step a, the reaction is refluxed for 24 hours.
In one embodiment of the invention, in the step a, the mixture is roasted at 500 ℃; and b, roasting at 600 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst of the invention adopts a specific cerium-zirconium solid solution as a carrier, and introduces an auxiliary agent, thereby obviously improving the selectivity and the carbon deposition resistance of the target product olefin. The catalyst has good carbon deposition resistance and obviously improved catalytic stability. And the preparation method is simple and has low cost and good industrial application prospect.
Drawings
FIG. 1 is a graph of the consumption rate of reactants and the production rate of ethylene in example 2.
FIG. 2 is a Raman spectrum of the catalyst used in example 2.
Detailed Description
The catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide takes CeZr solid solution as a carrier, Cr and an auxiliary agent are loaded on the carrier, the content of Cr is 8-15% and the content of the auxiliary agent is less than 10% based on 100% of the mass of the catalyst, and the molecular formula of the CeZr solid solution is CexZr1-xO2X is 0.1-0.9, and the auxiliary agent is at least one of Li, Na, K, Mg, Ca and Sr.
The catalyst adopts CeZr solid solution as a carrier, cerium is one of rare earth elements with the most abundant reserves and the cheapest price, and has better anti-carbon deposition capability because the cerium has good oxygen storage and release properties, and the addition of Zr can change the property of oxygen and adjust the acidity and alkalinity, so that the catalyst has the prospect of industrial application, and an auxiliary agent is introduced, wherein the content of the auxiliary agent is more than 0 and less than or equal to 10 percent, the selectivity of a target product olefin is obviously improved, the anti-carbon deposition capability of the catalyst is obviously improved, and the catalytic stability is obviously improved.
In one embodiment of the invention, the content of Cr is 9-11%, and the content of the auxiliary agent is 0.6-10%. In one embodiment of the invention, the content of Cr is 10% and the content of the auxiliary agent is 5%.
The lower alkane is an alkane with the carbon number less than or equal to 5, and in some embodiments, the lower alkane is ethane, propane or butane.
In one embodiment of the present invention, x is 0.3 to 0.7. In one embodiment of the invention, x is 0.7.
The CeZr solid solution can be prepared by the conventional method in the field, and in one embodiment of the invention, the CeZr solid solution is prepared by a uniform precipitation method.
The uniform precipitation method is characterized in that certain chemical reaction is utilized to slowly and uniformly release crystal-forming ions in a solution from the solution, and the concentration of a precipitator in the solution is controlled to ensure that the precipitate in the solution is in a balanced state, so that the precipitate is uniformly separated out. By adopting a uniform precipitation method, the carrier material with better performance can be prepared.
The method of loading the Cr and the auxiliary on the carrier can also adopt the method existing in the field, and in one embodiment of the invention, the Cr and the auxiliary are loaded on the carrier by adopting an incipient wetness impregnation method. Incipient wetness impregnation, i.e. suction-dry impregnation, isovolumetric impregnation, i.e. impregnation wherein a volume of impregnating solution is prepared equal to the pore volume of the support. The conventional initial impregnation operation in this field is applicable to the present invention and will not be described herein.
The second technical problem to be solved by the invention is to provide the preparation method of the catalyst for preparing the olefin by oxidizing the low-carbon alkane with the carbon dioxide.
The invention relates to a preparation method of a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide, which comprises the following steps:
a. preparation of CeZr solid solution: uniformly mixing cerium salt, zirconium salt, urea and water, carrying out reflux reaction for 20-30 h, carrying out solid-liquid separation, washing and drying a precipitate, and then roasting at 400-600 ℃ to obtain a CeZr solid solution;
b. mixing chromium salt, auxiliary agent salt and water to form an impregnation solution, placing a CeZr solid solution in the impregnation solution for impregnation, then removing, drying, and roasting at 500-700 ℃ to obtain a catalyst; the auxiliary salt is at least one of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt and strontium salt.
Water soluble salts commonly used in the art are suitable for use in the present invention. In a specific embodiment of the present invention, the cerium salt is cerium nitrate, the zirconium salt is zirconium nitrate, the chromium salt is chromium nitrate, the lithium salt is lithium nitrate, the sodium salt is sodium nitrate, the potassium salt is potassium nitrate, the magnesium salt is magnesium nitrate, the calcium salt is calcium nitrate, and the strontium salt is strontium nitrate.
In one embodiment of the present invention, in step a, the reaction is refluxed for 24 hours.
In one embodiment of the invention, in the step a, the mixture is roasted at 500 ℃; and b, roasting at 600 ℃.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
EXAMPLE 1 preparation of the catalyst
Preparation of cerium zirconium solid solution carrier: 2.89g of Ce (NO) was added to 200ml of the aqueous solution3)3·6H2O, 1.43g of Zr (NO)3)4·5H2O and 6g of urea were dissolved by stirring at room temperature. The solution was then transferred to a 500ml round bottom flask and warmed to 140 ℃ under reflux and held for 24 h. Suction filtration was then carried out, the precipitate was washed to neutrality and the solid obtained was dried at 100 ℃ for 12 h. Finally, roasting the mixture in air at 500 ℃ to obtain a carrier, wherein the carrier is named as Ce0.7Zr0.3O2。
Catalyst preparation by incipient wetness impregnation: cr is derived from Cr (NO)3)3·9H2O, K are from KNO3. Dissolving the quantitative metal salt substance by using deionized water to form the metal salt. The carrier was named Ce0.7Zr0.3O2Immersing in an immersion solution during immersionAfter the operation is finished, the solid is taken out and dried overnight at the temperature of 80 ℃, and then calcined at the temperature of 600 ℃ in the air to obtain the catalyst.
Wherein Cr (NO) is controlled3)3·9H2O and KNO3In a quantity such that different catalysts were obtained, wherein the catalyst having a Cr content of 10 wt.% and a K content of 0.6 wt.% was recorded as 0.6KCr/CZ, based on 100% catalyst content. The catalyst having a Cr content of 10 wt% and a K content of 1 wt% was designated as 1KCr/CZ, based on 100% catalyst. The catalyst having a Cr content of 10 wt% and a K content of 5 wt% was designated as 5KCr/CZ, based on 100% catalyst. The catalyst having a Cr content of 10 wt% and a K content of 10 wt% was designated as 10KCr/CZ, based on 100% catalyst. Catalysts with a Cr content of 10 wt.% and a K content of 0 wt.%, based on 100% catalyst content, i.e. catalysts which do not contain potassium nitrate in the impregnation solution, are denoted as Cr/CZ.
EXAMPLE 2 Oxidation of ethane with carbon dioxide to ethylene
The catalytic performance of each catalyst of example 1 was measured in a fixed bed atmospheric microreactor at a reaction temperature of 700 ℃ and a pressure of atmospheric pressure with a feed gas composition C2H6:CO2:N2Ar is 20:2:4:56, and the flow rate of the raw material gas is 30 ml/min. After stabilization, the conversion and selectivity are shown in Table 1.
The conversion rate is calculated by the following method:
wherein n isi,inThe amount of substance i, n, fed into the reactor within 1hi,outIs the amount of substance i in the product within 1h, said substance i being C2H6Or CO2。
The selectivity calculation method comprises the following steps:
wherein n isiThe amount of substance, Σ, which is the desired product olefin i in 1hiniThe total mass of the carbonaceous product.
TABLE 1
The consumption rate of the reactants and the production rate of ethylene in the reaction were monitored and the results are shown in FIG. 1. In the figure, a is Cr/CZ, b is 5KCr/CZ, and the graph shows that the time for reaching the stable state of 5KCr/CZ is faster, and the conversion rate and the selectivity are higher when the stable state is achieved. In the initial stage of the reaction, Cr/CZ showed higher C2H6And CO2Conversion of (2) (all about 47%), C2H4The selectivity was about 45%. It is stable after 15h, when stable, Cr/CZ is to C2H6Conversion and CO2The conversion was reduced by 20% and 24%, respectively. Although the initial conversion of 5KCr/CZ is low (C)2H635% of CO232%) but it reached a stability within 6h, with a loss of only 6% of conversion compared to Cr/CZ and, more importantly, with C2H4The selectivity eventually stabilized at a higher level (about 91%).
The raman spectrum of the catalyst after use is shown in fig. 2. In FIG. 2, a is Cr/CZ, b is 0.6KCr/CZ, c is 1KCr/CZ, d is 5KCr/CZ, and e is 10 KCr/CZ. As can be seen from the figure, no carbon species (no D and G bands) was detected by raman spectroscopy analysis, indicating that the catalyst of the present invention has significantly improved resistance to carbon deposition.
Example 3 preparation of propylene by oxidizing propane with carbon dioxide
In a fixed bed normal pressure microreactor, the catalyst of example 1 is used for catalyzing carbon dioxide to oxidize propane to prepare propylene, the reaction temperature is 550 ℃, the pressure is normal pressure, and the feed gas composition is C3H8:CO2:N2Ar is 20:2:4:56, and the flow rate of the raw material gas is 30 ml/min. After stabilization, the conversion and selectivity are shown in Table 2.
TABLE 2
Monitoring the rate of consumption of the reactants and the rate of ethylene production in the reaction found: the time for 5KCr/CZ to reach stability is faster, and the conversion rate and the selectivity are higher during the stability. In the initial stage of the reaction, Cr/CZ showed higher C2H6And CO2Conversion of (2) (all about 44%), C3H6The selectivity was about 46%. It only reaches stability after 18h, when stable, C3H8Conversion and CO2The conversion was reduced by 22% and 25%, respectively. Although the initial conversion of 5KCr/CZ is low (C)3H837% of CO239%) but stabilized within 5h, with a loss of only 7% in conversion compared to Cr/CZ and, more importantly, with C3H6The selectivity eventually stabilized at a higher level (about 89%).
Example 4
By the method of example 1, Ce (NO) was changed3)3·6H2O and Zr (NO)3)4·5H2The dosage of O is used to obtain Ce in the cerium-zirconium solid solution with different x valuesxZr1-xO2(x ═ 1.0, 0.9, 0.7, 0.5, and 0.3) as CeO2，Ce0.9Zr0.1O2、Ce0.7Zr0.3O2、Ce0.5Zr0.5O2And Ce0.3Zr0.7O2。
Control of Cr (NO) by incipient wetness impregnation3)3·9H2The amount of O, giving a catalyst containing 10% Cr, is respectively designated 10Cr/CeO2，10Cr/Ce0.9Zr0.1O2、10Cr/Ce0.7Zr0.3O2、10Cr/Ce0.5Zr0.5O2And 10Cr/Ce0.3Zr0.7O2。
The performance of the catalyst was measured by the method described in example 2, and the results are shown in Table 3.
TABLE 3
Visible, with CeO2Compared with the method, the method takes the cerium-zirconium solid solution as the carrier, so that the selectivity of the catalyst can be improved.
Claims (9)
1. The catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide is characterized in that: the catalyst takes CeZr solid solution as a carrier, Cr and an auxiliary agent are loaded on the carrier, the content of Cr is 8-15% and the content of the auxiliary agent is less than 10% based on 100% of the mass of the catalyst, and the molecular formula of the CeZr solid solution is CexZr1-xO2X is 0.1-0.9, and the auxiliary agent is at least one of Li, Na, K, Mg, Ca and Sr.
2. The catalyst for preparing olefin by oxidizing light alkane with carbon dioxide according to claim 1, wherein: the content of Cr is 9-11%, and the content of the auxiliary agent is 0.6-10%; preferably, the content of Cr is 10% and the content of the auxiliary agent is 5%.
3. The catalyst for preparing olefin by oxidizing light alkane with carbon dioxide according to claim 1, wherein: the lower alkane is ethane, propane or butane.
4. The catalyst for preparing olefin by oxidizing light alkane with carbon dioxide according to claim 1, wherein: x is 0.3 to 0.7; preferably x is 0.7.
5. The catalyst for preparing olefin by oxidizing light alkane with carbon dioxide according to claim 1, wherein: the carrier is prepared by a uniform precipitation method, and the Cr and the auxiliary agent are loaded on the carrier by an incipient wetness impregnation method.
6. The preparation method of the catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
a. preparation of CeZr solid solution: uniformly mixing cerium salt, zirconium salt, urea and water, carrying out reflux reaction for 20-30 h, carrying out solid-liquid separation, washing and drying a precipitate, and then roasting at 400-600 ℃ to obtain a CeZr solid solution;
b. mixing chromium salt, auxiliary agent salt and water to form an impregnation solution, placing a CeZr solid solution in the impregnation solution for impregnation, then removing, drying, and roasting at 500-700 ℃ to obtain a catalyst; the auxiliary salt is at least one of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt and strontium salt.
7. The method for preparing the catalyst for preparing the olefin by oxidizing the light alkane with the carbon dioxide as claimed in claim 6, wherein the method comprises the following steps: the cerium salt is cerium nitrate, the zirconium salt is zirconium nitrate, the chromium salt is chromium nitrate, the lithium salt is lithium nitrate, the sodium salt is sodium nitrate, the potassium salt is potassium nitrate, the magnesium salt is magnesium nitrate, the calcium salt is calcium nitrate, and the strontium salt is strontium nitrate.
8. The method for preparing the catalyst for preparing the olefin by oxidizing the light alkane with the carbon dioxide as claimed in claim 6, wherein the method comprises the following steps: in the step a, refluxing reaction is carried out for 24 hours.
9. The method for preparing the catalyst for preparing the olefin by oxidizing the light alkane with the carbon dioxide as claimed in claim 6, wherein the method comprises the following steps: in the step a, roasting at 500 ℃; and b, roasting at 600 ℃.
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