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CN115970673B - Chromium-based alkane dehydrogenation catalyst and preparation method thereof - Google Patents

Chromium-based alkane dehydrogenation catalyst and preparation method thereof Download PDF

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CN115970673B
CN115970673B CN202211660649.7A CN202211660649A CN115970673B CN 115970673 B CN115970673 B CN 115970673B CN 202211660649 A CN202211660649 A CN 202211660649A CN 115970673 B CN115970673 B CN 115970673B
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catalyst
chromium
alkane dehydrogenation
precursor
dehydrogenation catalyst
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CN115970673A (en
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梁衡
潘相米
韩伟
李扬
艾珍
张军
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Southwest Research and Desigin Institute of Chemical Industry
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Southwest Research and Desigin Institute of Chemical Industry
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention belongs to the field of alkane dehydrogenation catalysts, and particularly relates to a preparation method of a chromium-based alkane dehydrogenation catalyst. The catalyst prepared by the method comprises an active component Cr, a stabilizer A, an auxiliary agent B and a carrier, wherein A is one or more of Ti and Zr, B is one or more of alkali metal or alkaline earth metal, and through the preparation method provided by the invention, the pore canal of the catalyst carrier is firmer, the catalyst carrier has good high-temperature resistance and good regeneration stability.

Description

Chromium-based alkane dehydrogenation catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a chromium-based alkane dehydrogenation catalyst and a preparation method thereof.
Background
The alkane dehydrogenation technology has been industrialized, and currently used catalysts mainly have two types: pt-based catalysts and CrOx-based catalysts. Pt-based catalysts are too costly and sensitive to sulfur, olefins, and other poisons, and therefore require relatively stringent raw material requirements, requiring pretreatment of the raw material. The Cr-based catalyst has the advantages of low price, high alkane conversion rate and the like, but is easy to coke and deactivate quickly and needs to be regenerated repeatedly; the single-pass operation period of the industrial Cr-based catalyst is only 15-30 min, and the frequent burning regeneration greatly influences the physical and chemical structure of the catalyst, and finally leads to the deactivation of the catalyst. Firstly, the specific surface area of the catalyst decreases with the increase of the reaction time, the increase of the reaction temperature and the increase of the reduction-dehydrogenation-regeneration cycle times, and secondly, the frequent high-temperature regeneration easily causes the sintering of the active center of Cr and the migration of the surface phase Cr to the bulk phase, thereby forming a stable Cr 2O3-Al2O3 -type spinel structure and inactivating the catalyst.
CN 104148070 discloses a low-carbon alkane dehydrogenation catalyst containing framework silver, which adopts alumina containing silver as a carrier, chromium oxide as an active component, sodium, potassium, calcium, copper, zirconium, silver and the like as auxiliary agents, and can improve the stability and the anti-carbon capability of the catalyst. CN 103769156 discloses a dehydrogenation catalyst and a preparation method thereof, ammonia treatment alumina is adopted as a carrier, chromium is adopted as an active component, potassium, manganese, cobalt, iron, nickel, copper and the like are adopted as auxiliary agents, and the catalyst has the advantages of low content of chromium oxide, high activity, good propylene selectivity and the like. CN 102019178A reports a catalyst for preparing propylene by dehydrogenating propane, and preparation and application thereof, wherein the content of chromium oxide is 10-20%, the reaction temperature is 590 ℃, the absolute pressure is 0.105MPa, the conversion rate of propane is 40% when the reaction is carried out for 5min under the condition of airspeed of 900 hours -1, and the propylene selectivity is 85%. CN101940922B reports a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein chromium is used as an active metal component, chromium-containing alumina is used as a carrier, the weight content of the chromium oxide in the carrier is 2.0-15.0%, the activity of the catalyst is improved, and the like. CN101940922a reports a low-carbon alkane dehydrogenation catalyst, which takes Cr as an active component and alkali metal as an auxiliary agent, and the conversion rate of propane is 47% and the selectivity of propylene is about 89% when the reaction is carried out for 30 minutes at 645 ℃ and a liquid hourly space velocity of 600 hours < -1 > and normal pressure. The above patents mainly improve catalyst conversion and selectivity or single pass stability without concern for catalyst deactivation caused by cyclic regeneration at high temperatures.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chromium-based alkane dehydrogenation catalyst which is a novel Cr-based alkane dehydrogenation catalyst and has higher conversion rate and selectivity.
It is a further object of the present invention to provide a process for preparing the above catalyst.
In order to achieve the purpose of the invention, the following technical scheme is adopted in detail:
a chromium-based alkane dehydrogenation catalyst comprises an active component Cr, a stabilizer A, an auxiliary agent B and a carrier; the active component accounts for 10 to 35 percent of the total weight of the catalyst based on the oxide content; based on the content of oxide, the stabilizer A accounts for 0.1 to 5 percent of the total weight of the catalyst; the additive B accounts for 0.1 to 3 percent of the total weight of the catalyst based on the oxide content; the balance being carrier, the sum of the total mass percent is 100%.
Further, the oxide of the active component Cr is Cr 2O3, and the precursor material is chromium nitrate.
Further, the stabilizer A is any one or a mixture of two of Ti and Zr; the precursor of the stabilizer A is one or more of zirconium oxychloride, zirconyl nitrate and titanium tetrachloride.
Further, the auxiliary agent B is any one or a mixture of a plurality of alkali metals or alkaline earth metals; the precursor of the auxiliary agent B is nitrate or chloride of alkali metal or alkaline earth metal;
Further, the carrier is alumina; the precursor of the carrier is aluminum nitrate and aluminum trichloride.
As a preferred embodiment of the application, the preparation method of the chromium-based alkane dehydrogenation catalyst comprises the following steps:
a. Dissolving a precursor of an active component, a precursor of a stabilizer A and a precursor of a carrier in water, and uniformly stirring to obtain a solution; slowly dripping a precipitator to enable the pH value of the solution to be 9.0-11.0;
b. Heating the substance obtained in the step a to 50-90 ℃ and aging for 4-48 hours; then spray drying to obtain microsphere powder with peptization property;
c. Adding a proper amount of acid and a precursor solution of the auxiliary agent B into the powder obtained in the step B, uniformly mixing, extruding strips and forming; and then drying and roasting to obtain the catalyst.
Further, the solution in the step a is a saturated solution of aluminum ions.
Further, the precipitant is any one of ammonium carbonate and ammonium bicarbonate.
Further, the acid in the step c is any one of nitric acid and hydrochloric acid, and the mole number of the added acid is 3-20% of the total mole number of Al and Cr.
Preferably, the drying temperature in the step c is 80-120 ℃ and the drying time is 4-10 h; the roasting temperature is 600-1000 ℃ and the roasting time is 4-10 h.
The catalyst prepared by any one of the above methods has a specific surface area of less than 150m 2/g and a pore volume of less than 0.45ml/g.
Compared with the prior art, the invention has the following positive effects:
The acid is added into the powder, so that the powder can be sticky, the strength of the catalyst can be improved, the acid can also act with partial chromium precipitates, the distribution of the catalyst phase and the surface phase chromium is more reasonable, the action of the phase chromium and aluminum can be inhibited, the action of the surface phase chromium element and aluminum oxide can be inhibited, and the stability of the catalyst can be improved.
And secondly, the invention avoids pore canal blockage caused by chromium precursor impregnation, and the ammonium salt generated in the synthesis step is decomposed by high-temperature roasting to increase large pore canal, thereby facilitating rapid overflow of reaction products and improving selectivity of target products.
And thirdly, preparing an aluminum ion saturated solution and performing subsequent precipitation aging operation to obtain the catalyst with smaller specific surface area and smaller pore volume, so that the pore channel structure is more stable, and meanwhile, a stabilizer is added in the catalyst preparation process, so that the pore channel of the catalyst is not easy to collapse at high temperature, and the regeneration stability of the catalyst is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The test method of the catalyst evaluation result in the following examples is: 4.4g of the prepared catalyst is weighed, performance evaluation is carried out on a fixed bed device, the catalyst is fed in a volume ratio of propane to nitrogen of 1:1, the reaction temperature is 575 ℃, the mass space velocity of the propane is 0.7h -1, and the evaluation result is instantaneous data when the catalyst is fed for 5 min.
Example 1
Weighing 68.45g of chromium nitrate nonahydrate, 618.10g of aluminum nitrate nonahydrate and 5.82g of zirconium oxychloride octahydrate, adding a proper amount of water to enable the aluminum nitrate nonahydrate to be just completely dissolved, uniformly stirring, adding a proper amount of ammonium carbonate, adjusting the pH value to 9.5, then heating to 50 ℃, standing and aging for 24 hours, obtaining microsphere powder with peptization performance through spray drying (spray drying adopts the conventional technology in the industry), adding an aqueous solution containing 2.15g of potassium nitrate and 0.25mol of HNO 3 into the powder, extruding the mixture to form strips, drying at 80 ℃ for 10 hours, and roasting at 600 ℃ for 6 hours to obtain the catalyst;
The specific surface area of the catalyst was determined to be 143m 2 and the pore volume was determined to be 0.38ml/g. The evaluation result of the catalyst shows that: the propane conversion was 44.26% and the selectivity 90.33%.
Example 2
Weighing 94.77g of chromium nitrate nonahydrate, 210.55g of aluminum trichloride and 1.88g of zirconyl nitrate, adding a proper amount of water to enable the aluminum trichloride to be just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 10.2, then heating to 80 ℃, standing and aging for 12 hours, obtaining microsphere powder with peptization performance through spray drying, adding an aqueous solution containing 0.78g of magnesium nitrate hexahydrate and 0.71g of sodium chloride and 0.11mol of HCl, extruding to form, drying at 120 ℃ for 4 hours, and roasting at 750 ℃ for 8 hours to obtain a catalyst;
the specific surface area of the catalyst is 128m2, and the pore volume is 0.33ml/g. The evaluation result of the catalyst shows that: the propane conversion was 42.79% and the selectivity was 91.68%.
Example 3
Weighing 115.83g of chromium nitrate nonahydrate, 537.16g of aluminum nitrate nonahydrate, 3.42g of zirconyl nitrate and 2.80g of titanium tetrachloride, adding a proper amount of water to enable the aluminum nitrate nonahydrate to be just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH value to 10.8, then heating to 70 ℃, standing and aging for 36h, obtaining microsphere powder with peptization performance through spray drying, adding an aqueous solution containing 3.96g of calcium chloride and 0.15mol of HNO 3, extruding to form strips, drying at 100 ℃ for 6h, and roasting at 900 ℃ for 5h to obtain a catalyst;
the specific surface area of the catalyst is 98m2, and the pore volume is 0.37ml/g. The evaluation result of the catalyst shows that: the propane conversion was 43.79% and the selectivity was 92.74%.
Example 4
Weighing 136.89g of chromium nitrate nonahydrate, 192.50g of aluminum trichloride and 0.47g of titanium tetrachloride, adding a proper amount of water to enable the aluminum trichloride to be just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 9.2, then heating to 90 ℃, standing and aging for 7 hours, obtaining microsphere powder with peptization performance through spray drying, adding an aqueous solution containing 0.92g of lithium nitrate and 0.16mol of HCl, extruding to form strips, drying at 120 ℃ for 4 hours, and roasting at 800 ℃ for 5 hours to obtain a catalyst;
The specific surface area of the catalyst is 133m2, and the pore volume is 0.42ml/g. The evaluation result of the catalyst shows that: the propane conversion was 45.79% and the selectivity 90.21%.
Example 5
Weighing 94.77g of chromium nitrate nonahydrate, 588.67g of aluminum nitrate nonahydrate and 2.81g of zirconyl nitrate, adding a proper amount of water to enable the aluminum nitrate nonahydrate to be just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 10.4, then heating to 70 ℃, standing and aging for 48 hours, obtaining microsphere powder with peptization performance through spray drying, adding an aqueous solution containing 2.15g of potassium nitrate and 0.20mol of HNO 3, extruding to form strips, drying at 120 ℃ for 9 hours, and roasting at 950 ℃ for 7 hours to obtain a catalyst; the specific surface area of the catalyst is 92m2, and the pore volume is 0.35ml/g. The catalyst evaluation results were as follows:
Conversion rate Selectivity of
Initial initiation 45.42％ 92.45％
Regenerated ten times 45.69％ 92.40％
Fifty times of regeneration 45.02％ 92.68％
Regeneration one hundred times 45.73％ 92.78％
Regenerated twice and hundred times 45.23％ 92.36％
Comparative example 1
The difference from example 5 is that chromium nitrate nonahydrate is introduced by means of impregnation. The specific surface area of the catalyst is 82.48m 2/g and the pore volume is 0.24ml/g. The catalyst evaluation results were as follows
Conversion rate Selectivity of
Initial initiation 42.70％ 91.86％
Regenerated ten times 42.54％ 92.38％
Fifty times of regeneration 42.69％ 92.01％
Regeneration one hundred times 41.92％ 92.66％
Regenerated twice and hundred times 41.48％ 92.72％
As can be seen from the comparison of example 5 with comparative example 1, the catalyst prepared in example 5 has better stability and higher conversion.
Comparative example 2
Unlike example 5, the following is: the amount of water in which the aluminum nitrate nonahydrate solution was dissolved in comparative example 2 was 3 times the amount of water in the solution of example 5. Comparative example 2 catalyst had a specific surface area of 167m 2, a pore volume of 0.55ml/g, and the catalyst was evaluated as follows:
As can be seen from the comparison of example 5 with comparative example 2, the catalyst prepared in example 5 has better stability and higher selectivity.
Comparative example 3
The difference from example 5 is that the microsphere powder with peptization property is directly obtained by spray drying without standing and aging for 48 hours. The specific surface area of the catalyst is 172.4m 2/g, and the pore volume is 0.46ml/g.
Conversion rate Selectivity of
Initial initiation 47.42％ 91.33％
Regenerated ten times 46.69％ 91.69％
Fifty times of regeneration 43.08％ 92.97％
Regeneration one hundred times 41.43％ 93.06％
Regenerated twice and hundred times 40.31％ 93.22％
Example 5 compares with comparative example 3, and although comparative example 3 has higher initial activity, the regeneration stability is inferior to that of example 5.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (8)

1. The preparation method of the chromium-based alkane dehydrogenation catalyst is characterized in that the catalyst comprises an active component Cr, a stabilizer A, an auxiliary agent B and a carrier; the active component accounts for 10-35% of the total weight of the catalyst based on the content of oxide; based on the content of oxide, the stabilizer A accounts for 0.1-5% of the total weight of the catalyst; the additive B accounts for 0.1-3% of the total weight of the catalyst based on the content of oxide; the balance of the carrier, and the total mass is 100%; the stabilizer A is any one or a mixture of two of Ti and Zr; the auxiliary agent B is any one or a mixture of a plurality of alkali metals or alkaline earth metals;
The preparation method of the chromium-based alkane dehydrogenation catalyst comprises the following steps:
a. Dissolving a precursor of an active component, a precursor of a stabilizer A and a precursor of a carrier alumina in water, and uniformly stirring to obtain a solution; slowly dripping a precipitator to enable the pH value of the solution to be 9.0-11.0; the solution is a saturated solution containing aluminum ions; the precipitant is any one of ammonium carbonate and ammonium bicarbonate;
b. c, heating the material obtained in the step a to 50-90 ℃ and aging for 4-48 hours; then spray drying to obtain microsphere powder with peptization property;
c. Adding a proper amount of acid and a precursor solution of the auxiliary agent B into the powder obtained in the step B, uniformly mixing, extruding strips and forming; and then drying and roasting to obtain the catalyst.
2. The method for preparing a chromium-based alkane dehydrogenation catalyst according to claim 1, characterized in that: the oxide of the active component Cr is Cr 2O3, and the precursor material is chromium nitrate.
3. The method for preparing a chromium-based alkane dehydrogenation catalyst according to claim 1, characterized in that: the precursor of the stabilizer A is one or more of zirconium oxychloride, zirconyl nitrate and titanium tetrachloride.
4. The method for preparing a chromium-based alkane dehydrogenation catalyst according to claim 1, characterized in that: the precursor of the auxiliary agent B is nitrate or chloride of alkali metal or alkaline earth metal.
5. The method for preparing a chromium-based alkane dehydrogenation catalyst according to claim 1, characterized in that: the precursor of the carrier is aluminum nitrate or aluminum trichloride.
6. The method for preparing a chromium-based alkane dehydrogenation catalyst according to claim 1, characterized in that: the acid in the step c is any one of nitric acid and hydrochloric acid, and the mole number of the added acid is 3-20% of the total mole number of Al and Cr.
7. The method for preparing a chromium-based alkane dehydrogenation catalyst according to claim 1, characterized in that: the drying temperature in the step c is 80-120 ℃, and the drying time is 4-10 hours; the roasting temperature is 600-1000 ℃, and the roasting time is 4-10 h.
8. The catalyst prepared by the method according to any one of claims 1-7, wherein: the specific surface area of the catalyst is less than 150m 2/g, and the pore volume is less than 0.45ml/g.
CN202211660649.7A 2022-12-23 2022-12-23 Chromium-based alkane dehydrogenation catalyst and preparation method thereof Active CN115970673B (en)

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