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Catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene, and preparation method thereof

A catalyst technology for the dehydrogenation of ethylbenzene, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the problem of low potassium catalyst activity and low stability problem, achieve the effect of enhancing anti-reduction ability, reducing acidity and improving stability

Active Publication Date: 2016-07-13
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The technical problem to be solved by the present invention is the low activity and stability of the low-potassium catalyst existing in the prior art under the low water ratio reaction process. Hydrogen to styrene catalyst

Method used

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  • Catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene, and preparation method thereof
  • Catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene, and preparation method thereof
  • Catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene, and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Weigh 300g iron oxide red, 73.5g potassium carbonate, 5g zinc oxide, 5g manganese dioxide, 5g lead dioxide and dry mix for 1 hour, then roast at 600°C for 2 hours, add 83g cerium oxalate, 28.9g Ammonium tetramolybdate, 25g magnesium oxide, 35.6g calcium carbonate, and 30g carboxymethyl cellulose, dry powder mixed for 2 hours, add 130mL deionized water and knead for about 1 hour to form a dough-like material suitable for extrusion, extrude and cut into pellets into particles with a diameter of about 3 mm and a length of 6-8 mm; aged at room temperature for 12 hours, dried at 120°C for 4 hours, placed in a muffle furnace at a high temperature of 900°C for 6 hours to obtain a catalyst precursor, and measured the precursor with a 500mL measuring cylinder Volume: Prepare a mixed solution consisting of 7.9g rubidium nitrate, 6.9g cesium nitrate and 10g lanthanum nitrate, which has the same volume as the catalyst precursor, and then use the equal volume impregnation method to l...

Embodiment 2

[0032] Weigh 340g iron oxide red, 66.2g potassium carbonate, 2.5g zinc oxide, 2.5g manganese dioxide, 2.5g lead dioxide dry mix for 2 hours, then roast at 750°C for 4 hours, then add 83g cerium oxalate, 17.2 g ammonium tetramolybdate, 10g magnesium oxide, 17.8g calcium carbonate and 30g carboxymethyl cellulose, after mixing the dry powder for 2 hours, add 130mL deionized water and knead for about 1 hour to form a dough-like material suitable for extrusion, extrude and cut into pellets into particles with a diameter of about 3 mm and a length of 6-8 mm; aged at room temperature for 12 hours, dried at 120°C for 4 hours, placed in a muffle furnace at a high temperature of 900°C for 6 hours to obtain a catalyst precursor, and measured the precursor with a 500mL measuring cylinder Volume; prepare rubidium nitrate, cesium nitrate and lanthanum nitrate solutions with a concentration of 0.1mol / L, the dosages are respectively 15.8g of rubidium nitrate, 6.9g of cesium nitrate, and 15g of...

Embodiment 3

[0034] The preparation method of the catalyst of Examples 3-9 is the same as that of Example 1, and the composition of the catalyst is shown in Table 1. In the preparation process, embodiment 3 does not add porogen, embodiment 4 adds the carboxymethyl cellulose of catalyst weight 5%, adds the polystyrene microsphere of catalyst weight 8% in embodiment 5, adds catalyst weight in embodiment 6 2% graphite, add the carboxymethyl cellulose of catalyst weight 10% in embodiment 7, add the graphite of catalyst weight 1% in embodiment 8, add the carboxymethyl cellulose of catalyst weight 6 in embodiment 9.

[0035] The catalyst composition of table 1 embodiment 1~9

[0036]

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Abstract

The invention relates to a catalyst used for low steam-to-oil ratio ethylbenzene dehydrogenation to prepare styrene. The catalyst comprises, by mass, 60-80 parts of iron oxide by Fe2O3, 5-15 parts of potassium oxide by K2O, 5-15 parts of cerium oxide by Ce2O3, 1-10 parts of molybdenum oxide by MoO3, 1-10 parts of magnesium or / and calcium oxide by MgO or / and CaO respectively, 1-5 parts of at least one of alkali metal oxides of Rb and Cs, respectively by Rb2O and Cs2O, wherein the alkali metal oxides are modified on the surface of the catalyst in a salt solution form; and light rare earth metal oxides of La, Pr and Nd without Ce, and oxides of Mn, Zn and Pb. The catalyst has a high activity and a good stability under a low steam-to-oil ratio.

Description

technical field [0001] The invention relates to a catalyst and a preparation method for preparing styrene by dehydrogenating ethylbenzene at a low water ratio. Background technique [0002] The catalytic dehydrogenation reaction of ethylbenzene is a reversible process with increased number of molecules and strong endothermicity, which needs to be carried out under high temperature and low pressure reaction conditions. In order to increase the conversion rate of ethylbenzene and the yield of styrene in the ethylbenzene dehydrogenation reaction, a large amount of superheated steam is usually introduced into the process in industry. Water vapor mainly plays three roles, (1) as a heat source, providing heat for high-temperature reactions, avoiding heating ethylbenzene to a higher temperature, and inhibiting the occurrence of side reactions; (2) as a diluent, reducing the partial pressure of ethylbenzene , prompting the reaction to move toward the product; (3) a water-gas reacti...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889C07C15/46C07C5/333
Inventor 印会鸣姚文君王继龙王涛王学丽胡晓丽柏介军林宏边虎石岚仇国贤王兴梅
Owner PETROCHINA CO LTD
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