CN104888817A - Low-water-ratio ethylbenzene dehydrogenation catalyst - Google Patents

Low-water-ratio ethylbenzene dehydrogenation catalyst Download PDF

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Publication number
CN104888817A
CN104888817A CN201510278048.3A CN201510278048A CN104888817A CN 104888817 A CN104888817 A CN 104888817A CN 201510278048 A CN201510278048 A CN 201510278048A CN 104888817 A CN104888817 A CN 104888817A
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China
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catalyst
chloride
water
grams
dehydrogenation catalyst
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CN201510278048.3A
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Chinese (zh)
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廖仕杰
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廖仕杰
苏州拓瑞特新材料有限公司
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Priority to CN201510278048.3A priority Critical patent/CN104888817A/en
Publication of CN104888817A publication Critical patent/CN104888817A/en

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Abstract

The invention discloses a low-water-ratio ethylbenzene dehydrogenation catalyst which comprises the following components in percentage by weight: 60-85% of Fe2O3, 3-25% of K2O, 0.2-5% of MoO3, 3-20% of CeO2 and the balance of compounds or salts containing Cl. The low-water-ratio ethylbenzene dehydrogenation catalyst has high selectivity and activity and good stability under a low-water-ratio condition.

Description

A kind of ethylbenzene dehydrogenation catalyst with low water ratio

Technical field

The present invention relates to Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst technical field, particularly a kind of ethylbenzene dehydrogenation catalyst with low water ratio.

Background technology

Ethylbenzene dehydrogenation is strong heat absorption, the reversible reaction increasing molecule, and industrial usual employing water vapour makes diluent to reduce ethylbenzene dividing potential drop, impels reaction to move to product direction.Water vapour has following effect in the reaction:

(1) heat reaction raw materials to temperature required, avoid ethylbenzene to be directly heated to higher temperature, suppress the generation of side reaction, improve selective;

(2) additional heat, in order to avoid lower the temperature due to endothermic heat of reaction;

(3) constantly got rid of the carbon deposit on catalyst by water gas reaction, make catalyst automatic regeneration.

But water vapour addition is subject to reaction system authorized pressure falls the restriction with these two factors of energy consumption, advanced ethylbenzene dehydrogenation technique is all pursued and is obtained higher styrene yield with the lower water ratio mass ratio of water vapour and ethylbenzene (in the charging), and adopting low water than operating is one of styrene device important measures of saving energy and reduce the cost.

The Fe-series catalyst that catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene is take iron oxide as main active component, potassium oxide is main co-catalyst, potassium increases the activity of iron oxide with can becoming the order of magnitude, and can promote that carbon deposit is got rid of, made catalyst automatic regeneration by water gas reaction, at low water than under condition, due to the minimizing of steam vapour amount in reaction system, system reducing is caused to strengthen, many potassium ferrites in catalyst decompose under the effect of reducing atmosphere, potassium ion runs off from this compound, thus causes the decline of catalyst choice.If general catalyst carries out ethylbenzene dehydrogenation reaction under water ratio (water/ethylbenzene) is lower than 2.0 (weight), the selective variation of catalyst, although energy consumption reduces, material consumption but increases greatly.

To this, according to related documents report up to now, scientific research personnel had done a lot of trial, after published European patent 0177832 reports the magnesia adding 1.8-5.4% (weight) in the catalyst, catalyst can show stable premium properties at water under lower than 2.0 (weight), but the potassium content of this catalyst is higher; Add with kaliophilite Multiple salts forms as published United States Patent (USP) 4535067 reports a part of potassium in catalyst, but this catalyst 614 ± 2 DEG C time, conversion ratio is less than 65%, selective the highest by 93%, singly can not receive 60%, selective relatively low.

Therefore, while how reducing energy consumption in low water is than course of reaction, maintain or improve the selective of catalyst, reduce material consumption is the target that researcher makes great efforts always.

Summary of the invention

Based on catalyst for phenylethylene dehydrogenation in prior art at low water than poor selectivity under condition, active low problem, the object of the invention is to provide a kind of ethylbenzene dehydrogenation catalyst with low water ratio, this catalyst is used for ethylbenzene dehydrogenation reaction to prepare in styrene engineering and there is low water than good and feature that activity is high selective under condition, enhances productivity.

In order to overcome the deficiencies in the prior art, technical scheme provided by the invention is:

A kind of ethylbenzene dehydrogenation catalyst with low water ratio, comprises following component according to percentage by weight:

a)Fe 2O 3:60~85%;

b)K 2O:3~25%;

c)MoO 3:0.2~5%;

d)CeO 2:3~20%;

E) surplus is the compound or the salt that contain Cl.

In preferred technical scheme, the compound of described Cl is at least one in the chloride of the chloride of iron, the chloride of potassium, the chloride of cerium, the chloride of calcium or magnesium.

In preferred technical scheme, chloride weight percent meter consumption is 0.5 ~ 500ppm.

In preferred technical scheme, chloride weight percent meter consumption is 1 ~ 100ppm.

The raw materials of the catalyst that the present invention relates to is: Fe 2o 3by iron oxide red (Fe 2o 3) and iron oxide yellow (Fe 2o 3h 2o) form, the proportioning of iron oxide red and iron oxide yellow is Fe 2o 3: Fe 2o 3h 2o=0.2 ~ 5: 1, are preferably 1 ~ 4.5: 1; K used adds with sylvite or hydroxide form; Ce used adds with oxide, hydroxide or decorations salt form; Mo used adds with its salt or oxide form; Cl used adds in a chloride-form.In preparation process of the present invention, except catalyst body composition, also should add perforating agent, perforating agent can be selected from graphite, polystyrene microsphere, carboxymethyl cellulose, and its addition is the 1-6% of total catalyst weight.

The preparation method of the catalyst that the present invention relates to is: to weigh needed raw material and perforating agent according to proportioning, deionized water is added after mixing, make the paste that there is viscosity, be applicable to extrusion, the particle that diameter is 3mm, length is 8 ~ 10mm is become through extrusion, pelletizing, then dry 24h under 60 ~ 120 DEG C of conditions, finally under 400 ~ 1000 DEG C of conditions, roasting 4h obtains finished catalyst.

Compared with prior art, advantage of the present invention is:

The present invention by adding compound or the salt of Cl in iron-potassium-cerium-molybdenum catalyst system, the acid site of catalyst can be poisoned, suppress the side reaction occurred at catalyst acid center, improve catalyst in selective than under condition of low water, and make catalyst have higher activity, greatly enhance productivity.

Detailed description of the invention

Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.

Embodiment 1

120.0 grams of iron oxide reds, 60.0 grams of iron oxide yellows, 53 grams of potash, 66 grams of cerous carbonates, 3 grams of ammonium molybdates, 0.1 gram of iron chloride, 10.6 carboxymethyl celluloses are stirred 1 hour in kneading machine, add deionized water, stir 0.5 hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 8 ~ 10 millimeters, put into baking oven, 80 DEG C are dried 2 hours, 120 DEG C are dried 2 hours, are then placed in muffle furnace, roasting 4 hours obtained catalyst under 900 DEG C of conditions.

Obtained catalyst carries out activity rating in isotherm formula fixed bed, detailed process is: deionized water and ethylbenzene are inputted preheating mixer through measuring pump respectively, preheating enters reactor after being mixed into gaseous state, reactor is the stainless steel tube of 1 cun, the interior catalyst that can fill 100ml particle diameter 3mm, reactor adopts the temperature needed for electric-heating-wire-heating to reaction, the reactant flowed out by reactor with gas chromatographic analysis its composition, and adopts the conversion ratio of following formulae discovery ethylbenzene and cinnamic selective after water condensation:

100ml catalyst is loaded reactor, normal pressure, liquid air speed 1.0 hours -1, 620 DEG C, carry out activity rating under water ratio (weight) 1.5 condition, test result lists in table 1.

Embodiment 2

Other are identical with embodiment 1, and difference is that the raw material of Kaolinite Preparation of Catalyst is in example 2 305 grams of iron oxide reds, 100 grams of iron oxide yellows, 80 grams of potash, 78 grams of cerous nitrates, 12 grams of ammonium molybdates, 0.05 gram of potassium chloride, 15 grams of carboxymethyl celluloses.According to the activity of the evaluation method evaluate catalysts of embodiment 1 after obtained catalyst, test result is in table 1.

Embodiment 3

Other are identical with embodiment 1, and difference is that the raw material of Kaolinite Preparation of Catalyst is in embodiment 3 150 grams of iron oxide reds, 100 grams of iron oxide yellows, 108 grams of potash, 56 grams of cerium oxalates, 5 grams of ammonium molybdates, 0.02 gram of cerium chloride, 10 grams of carboxymethyl celluloses.According to the activity of the evaluation method evaluate catalysts of embodiment 1 after obtained catalyst, test result is in table 1.

Embodiment 4

Other are identical with embodiment 1, and difference is that the raw material of Kaolinite Preparation of Catalyst is in example 4 200 grams of iron oxide reds, 90 grams of iron oxide yellows, 46 grams of potash, 122 grams of cerium oxalates, 17 grams of ammonium molybdates, 0.005 gram of sodium chloride, 15 grams of carboxymethyl celluloses.According to the activity of the evaluation method evaluate catalysts of embodiment 1 after obtained catalyst, test result is in table 1.

Consisting of of the various embodiments described above catalyst:

Comparative example 1

According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is not adding iron chloride.Obtained catalyst is according to the activity of the evaluation method evaluate catalysts of embodiment 1, and test result is in table 1.

Comparative example 2

According to the method Kaolinite Preparation of Catalyst of embodiment 2, difference is not adding potassium chloride.Obtained catalyst is according to the activity of the evaluation method evaluate catalysts of embodiment 1, and test result is in table 1.

Comparative example 3

According to the method Kaolinite Preparation of Catalyst of embodiment 3, difference is not adding cerium chloride.Obtained catalyst is according to the activity of the evaluation method evaluate catalysts of embodiment 1, and test result is in table 1.

Comparative example 4

According to the method Kaolinite Preparation of Catalyst of embodiment 4, difference is not adding sodium chloride.Obtained catalyst is according to the activity of the evaluation method evaluate catalysts of embodiment 1, and test result is in table 1.

Above-mentioned comparative example obtains catalyst and consists of:

Table 1 catalytic dehydrogenation performance comparison

Table 2 catalyst stabilization performance compares

From the test result of above-described embodiment and comparative example relatively, catalyst for phenylethylene dehydrogenation of the present invention is with Fe 2o 3, K 2o, CeO 2, MoO 3for main component, by adding the compound of chlorine, obtained catalyst than having high selectivity and activity under condition, and has good stability at low water.

Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to Spirit Essence of the present invention or modification, all should be encompassed within protection scope of the present invention.

Claims (4)

1. an ethylbenzene dehydrogenation catalyst with low water ratio, is characterized in that comprising following component according to percentage by weight:
a)Fe 2O 3:60~85%;
b)K 2O:3~25%;
c)MoO 3:0.2~5%;
d)CeO 2:3~20%;
E) surplus is the compound or the salt that contain Cl.
2. ethylbenzene dehydrogenation catalyst with low water ratio according to claim 1, is characterized in that: the compound of described Cl is at least one in the chloride of the chloride of iron, the chloride of potassium, the chloride of cerium, the chloride of calcium or magnesium.
3. ethylbenzene dehydrogenation catalyst with low water ratio according to claim 1, is characterized in that: chloride weight percent meter consumption is 0.5 ~ 500ppm.
4. ethylbenzene dehydrogenation catalyst with low water ratio according to claim 3, is characterized in that: chloride weight percent meter consumption is 1 ~ 100ppm.
CN201510278048.3A 2015-05-27 2015-05-27 Low-water-ratio ethylbenzene dehydrogenation catalyst CN104888817A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4341912A (en) * 1976-10-01 1982-07-27 Mitsubishi Petrochemical Co. Ltd. Process for producing alkenyl-substituted aromatic compounds and catalyst therefor
CN1589964A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation
CN102728371A (en) * 2011-04-15 2012-10-17 廖仕杰 High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4341912A (en) * 1976-10-01 1982-07-27 Mitsubishi Petrochemical Co. Ltd. Process for producing alkenyl-substituted aromatic compounds and catalyst therefor
CN1589964A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation
CN102728371A (en) * 2011-04-15 2012-10-17 廖仕杰 High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof

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