Process for dehydrogenating alkanes to olefins

A technology for alkane dehydrogenation and olefin production, applied in chemical instruments and methods, hydrocarbons, hydrocarbons, etc., can solve the problems of no significant improvement in overall performance, high-temperature instability of chromium species, high cost of precious metals, etc. , to achieve the effect of simple operation, inhibition of coking, and improvement of selectivity

Active Publication Date: 2020-02-07
CHINA UNIV OF PETROLEUM (BEIJING)
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

Commercial dehydrogenation catalysts are divided into two categories, namely Pt-Sn / Al 2 o 3 Noble metal catalysts and CrO x -K / Al 2 o 3 Metal oxide catalysts, two types of commercial catalysts have significant dehydrogenation activity, but there are also some disadvantages, such as the high cost of noble metals, the high-temperature instability of chromium species, the toxicity of high-valent chromium species, and the two catalysts are prone to dehydrogenation due to coking. Deactivation, frequent regeneration is required, these problems restrict the development of dehydrogenation process, therefore, the research on dehydrogenation catalyst still needs continuous improvement, by adjusting the acidity of the catalyst, improving the dispersion of active components, or improving the preparation of the catalyst method to improve the thermal stability and anti-coking ability of the catalyst and prolong the service life of the catalyst
[0004] For a long time, a lot of research has focused on the improvement of the deactivation and lifetime of the two existing commercial dehydrogenation catalysts, but their overall performance has not been significantly improved

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  • Process for dehydrogenating alkanes to olefins
  • Process for dehydrogenating alkanes to olefins
  • Process for dehydrogenating alkanes to olefins

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preparation example Construction

[0033] The present invention also provides a preparation method of the catalyst, which is characterized in that the method comprises the following steps:

[0034] 1) Dry pretreatment of carbon material as template agent;

[0035] 2) Prepare a mixed aqueous solution of metal M salt and Zr salt;

[0036] 3) Add the mixed aqueous solution prepared in step 2) dropwise to the carbon material in step 1), and stir the resulting mixture to obtain a catalyst precursor;

[0037] 4) Drying and calcining the catalyst precursor in step 3) to obtain the catalyst MZr m O n .

[0038] In an embodiment of the present invention, the carbon material is selected from activated carbon or carbon black, such as granular activated carbon CGP, carbon black BP2000 or FW200; preferably carbon black, which has a specific surface area of ​​1100-1600 m 2 .g -1 , Preferably 1300-1500m 2 .g -1 The pore volume is 2-5mL / g, preferably 3-5mL / g. The carbon material can be prepared by a method known to those skilled in the...

Embodiment 1

[0082] Put Cu(NO 3 ) 2 ·3H 2 O and ZrO (NO 3 ) 2 ·2H 2 O was prepared with deionized water to form a mixed aqueous solution of metal salt with a concentration of 0.15 mol / L, in which the molar ratio of Cu and Zr was 1:5. Then, it was sonicated at 40°C for 1 hour to obtain a clear solution. At room temperature 22°C, take 6g carbon material BP2000 and add 23.32g metal salt aqueous solution dropwise, stir for 1 hour, dry overnight at room temperature, dry at 80°C for 5 hours, and calcinate at 550°C for 20 hours. The obtained catalyst is denoted as CuZr 5 O n . The catalyst needs to be at 580℃, H 2 / N 2 Pre-reduction treatment under the atmosphere for 2 hours. See Table 1 for activity evaluation data.

Embodiment 2

[0084] Put Cu(NO 3 ) 2 ·3H 2 O and ZrO (NO 3 ) 2 ·2H 2 O is formulated with deionized water to form a mixed aqueous solution of metal salt with a concentration of 0.15 mol / L, in which the molar ratio of Cu and Zr is 1:10. Then, it was sonicated at 40°C for 1 hour to obtain a clear solution. At room temperature 22℃, take 6g carbon material BP2000 and add 23.44g metal salt aqueous solution dropwise, stir for 75 minutes, dry overnight at room temperature, dry at 80℃ for 5h, and calcinate at 550℃ for 20 hours. The obtained catalyst is denoted as CuZr 10 O n . The catalyst needs to be at 580℃, H 2 / N 2 Pre-reduction treatment under the atmosphere for 2 hours. See Table 1 for activity evaluation data.

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Abstract

The invention relates to an olefin catalyst produced through paraffin dehydrogenation. The olefin catalyst is composed of oxide materials with a general formula (I), MZrmOn... (I), wherein respectivedefinitions of variables are as follows: M represents a low-valent doped metal Mdelta<+>, and delta is equal to 1, 2 or 3; m is a stoichiometric coefficient of Zr and is 1-20, preferably 1-10, more preferably 3-7; n is a stoichiometric coefficient of elemental oxygen and is determined by virtue of the stoichiometric coefficient of elements in the I except the oxygen and charge numbers thereof. Theinvention further relates to a preparation method and application of the catalyst.

Description

Technical field [0001] The invention relates to a catalyst for preparing olefins by dehydrogenation of alkanes, and a preparation method and application thereof. Background technique [0002] Low-carbon olefin molecules, such as propylene and isobutylene, can participate in many different types of chemical reactions due to their own active double bonds. They are important basic chemical raw materials and are mainly used to produce polymers, antioxidants, coatings, dyes, and gasoline. High value-added chemical products such as additives. Low-carbon olefins have important use value and broad application prospects, but they lack natural sources. Traditional low-carbon olefin production processes mainly include: catalytic cracking and steam cracking of petrochemical fuels. However, product olefins obtained by two traditional process technologies The purity is not high, and even after separation, the product olefin obtained cannot meet the rising market demand. In addition, due to t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/72B01J23/06B01J37/08B01J37/18C07C11/09C07C5/333
CPCB01J23/002B01J23/06B01J23/72B01J37/0018B01J37/08B01J37/18C07C5/3332C07C2523/06C07C2523/72C07C11/09
Inventor 柯明刘洋宋昭峥张蕾于涵夏成杰王奇
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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