CN1927458A - Catalyst for ethylbenzene dehydrogenation-hydroxide reaction - Google Patents
Catalyst for ethylbenzene dehydrogenation-hydroxide reaction Download PDFInfo
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- CN1927458A CN1927458A CNA2005100294608A CN200510029460A CN1927458A CN 1927458 A CN1927458 A CN 1927458A CN A2005100294608 A CNA2005100294608 A CN A2005100294608A CN 200510029460 A CN200510029460 A CN 200510029460A CN 1927458 A CN1927458 A CN 1927458A
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Abstract
The invention relates to a catalyst used to hydroxide in the ammonium hydroxide process of ethylbenzene. Wherein, it adds rare-earth element into platinum and tin system, to improve the hydrogen transfer rate and the selectivity of aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction.
Background technology
Styrene is important basic organic, is mainly used in to produce PS, ABS, materials such as SBR, SMA, and these materials all have important purposes at industrial circles such as automobile making, household electrical appliance, weaving, building materials.At present, cinnamic in the world production method has three kinds of ethylbenzene catalytic dehydrogenation methods, styrene and propylene oxide co-production method, oxidative dehydrogenation of ethylbenzene method.Wherein the ethylbenzene catalytic dehydrogenation method is the styrene main production methods, accounts for 90% of production of styrene ability.
It is the endothermic reaction that a molecular number increases that ethylbenzene dehydrogenation generates styrene, from thermodynamics.Reduce system pressure, improve system temperature reacting favourable.But be subjected to the restriction of thermodynamical equilibrium and reasonability economically, improve temperature merely, reduce pressure and can't meet the demands.To the eighties in last century, Uop Inc. of the U.S. has developed a kind of new technology of ethylbenzene dehydrogenation-hydroxide.It utilizes the reaction mechanism of ethylbenzene dehydrogenation, with the hydrogen of one of dehydrogenation product oxidation catalyst,, thereby break original chemical balance with the oxygen reaction that adds by high selectivity, it is moved to helping generating cinnamic direction, can increase substantially the conversion per pass of ethylbenzene; Because oxyhydrogen reaction is emitted a large amount of heat, can provide a part of dehydrogenation reaction required heat again simultaneously, reduce energy consumption.The technology that is adopted briefly is divided into three sections flow processs of dehydrogenation-hydroxide-dehydrogenation, and promptly material ethylbenzene carries out dehydrogenation reaction through first section dehydrogenation bed earlier; Reacted dehydrogenated tail gas mixes with the minor amounts of oxygen of interpolation after the oxidation catalyst bed carries out hydroxide reaction, hydrogen partial and oxygen in the dehydrogenated tail gas react, and carry out the dehydrogenation reaction second time through second section dehydrogenation bed again after the temperature raising of the heat of emitting with gaseous mixture.
One of key technology of ethylbenzene dehydrogenation-hydroxide technology is a hydro-oxidation catalyst.Because the introducing generation oxidation reaction of minor amounts of oxygen, not only to provide enough heats for dehydrogenation reaction, and can not enter hypomere dehydrogenation bed with dehydrogenated tail gas, to cause the oxidational losses of a part of aromatic hydrocarbons inevitably simultaneously, and in the technology of ethyl benzene dehydrogenation preparation of styrene, the cost of raw material accounts for more than 90% of totle drilling cost, if the oxidation selectivity of aromatic hydrocarbons is too high, then can cause a large amount of losses of raw material, therefore require this catalyst to have the conversion ratio of very high oxygen and lower arene oxidizing selectivity, that is to say, oxygen is reacted fully with hydrogen as much as possible, and avoid reacting with aromatic hydrocarbons.According to the characteristics of high selectivity, high conversion, the ethylbenzene dehydrogenation-hydroxide catalyst is selected for use with similar α-Al
2O
3Inert inorganic material etc. low BET surface, low pore volume is a carrier, carried noble metal-oxide catalyst that oxides such as carried noble metal Pt or Pd and Sn, Li form.
Introduced PtSnLi/Al among patent US4914249 and the US4812597
2O
3Catalyst is used for the hydroxide reaction of ethylbenzene dehydrogenation process, and wherein Li also can substitute with other alkali metal or alkaline-earth metal, adopts α-Al
2O
3As carrier.Introduced the oxide that adopts Sn, Ti, Ta, Nb or their mixture among the patent US5994606 as carrier, the catalyst of supporting Pt or Pd is used for the hydroxide reaction of ethylbenzene dehydrogenation process.US5001291 adopts the catalyst of noble metals such as load P d, Pt, Rh or Ru on the oxide of tin, is used for the hydroxide reaction of ethylbenzene dehydrogenation process.
The catalyst of above patent introduction is when being actually used in ethylbenzene dehydrogenation-hydroxide reaction, and oxygen conversion is lower, and the arene oxidizing selectivity is higher.Oxygen conversion and arene oxidizing selectivity are two important indicators in the hydroxide reaction process.If there is the unnecessary oxygen that does not react to enter follow-up dehydrogenation workshop section, will cause the reaction that is unfavorable for dehydrogenation in the hydroxide stage, therefore require oxygen to transform as far as possible fully, i.e. the conversion ratio height of oxygen; The arene oxidizing selectivity is meant the selectivity of aromatic hydrocarbons and oxygen generation side reaction, and selectivity is low more, and then the loss late of aromatic hydrocarbons is low more, therefore requires the oxidation selectivity of aromatic hydrocarbons low as far as possible.
Summary of the invention
Technical problem to be solved by this invention is lower, the arene oxidizing selectivity problem of higher of oxygen conversion that existing ethylbenzene dehydrogenation-hydroxide catalyst exists in ethylbenzene dehydrogenation-hydroxide reaction, and a kind of new catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction is provided.This catalyst has optionally advantage of higher oxygen conversion and lower arene oxidizing in hydroxide reaction.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction comprises following component by weight percentage:
(a) 0.01～1% platinum;
(b) oxide of 0.01～2% tin;
(c) oxide of 0.1～10% rare earth element;
(d) 88～99% to being reacted into the carrier of inertia.
In the technique scheme, in the catalyst by weight percentage the consumption preferable range of platinum be 0.05～0.3%, more preferably scope is 0.08～0.2%; The oxide consumption preferable range of tin is 0.05～1%, and more preferably scope is 0.1～0.5%; The oxide consumption preferable range of rare earth element is 0.5～5%, and more preferably scope is 1～2%.The carrier preferred version of inertia is selected from least a in Alpha-alumina, silica, cyanines green stone, mullite or the spinelle, and more preferably scheme is Alpha-alumina or cyanines green stone.Also contain 0.01～1% the alkali-metal oxide that is selected from by weight percentage in the catalyst, its consumption preferable range is 0.05～0.5%, and more preferably scope is 0.2～0.4%.The alkali metal preferred version is selected from lithium or sodium.
The Preparation of catalysts method of using among the present invention is as follows:
(a) the alkali-metal compound of compound and IA family of the compound of the compound of the platinum of a certain amount of solubility, tin, rare earth element is dissolved in a certain amount of deionized water is mixed with dipping solution;
(b) carrier is flooded with above-mentioned dipping solution;
(c) after the catalyst precarsor drying that obtains was handled, roasting obtained finished catalyst in 0.5～24 hour in 400～700 ℃ air.
The range of reaction temperature that ethylbenzene dehydrogenation-hydroxide catalyst of the present invention is adapted to is 500～700 ℃, and reaction pressure is absolute pressure 0.1～10 standard atmospheric pressure; The reaction atmosphere that is adapted to is for the organic matter hydrocarbon vapours that comprises except that dehydrogenation reaction, water vapour, the hydrogen, also is included in the mist of the oxygen that adds before the oxidation reaction, nitrogen or air etc.
The catalyst that makes as stated above carries out activity rating in normal pressure isotherm formula fixed bed, for hydro-oxidation catalyst performance evaluation, the summary process is as follows:
Raw material aromatic hydrocarbons and deionized water preheating in measuring pump input preheater respectively with preparing mix with hydrogen, oxygen and the nitrogen imported through flowmeter respectively in blender after the preheating, enter reactor together.The raw material composition sees Table 1.
Table 1 normal pressure isotherm formula fixed bed hydroxide reaction raw material and composition
| Raw material | Molar content % |
| Benzene toluene ethylbenzene styrene water hydrogen and oxygen nitrogen | 0.07 0.15 6.12 2.45 87.02 2.79 1.29 0.11 |
Reactor adopts the heating wire heating, makes it stable under reaction temperature.Reactor is the stainless steel tube of 25 millimeters of internal diameters, loads 30 milliliters, particle diameter and be 4.0 millimeters hydro-oxidation catalyst.Reacted product water condensation, after gas-liquid separation with gas chromatograph analysis composition separately.
The evaluating catalyst condition is as follows in the isotherm formula fixed bed reactors: reaction pressure is normal pressure, liquid air speed 1.0 hours
-1, 580 ℃ of reaction temperatures.
Oxygen conversion involved in the present invention and aromatic hydrocarbons combustion selective computing formula are as follows:
In the catalyst system and catalyzing of the present invention, owing to added rare earth oxide, the catalyst oxygen conversion ratio that overcomes in the previous patent is lower, and the higher shortcoming of arene oxidizing selectivity, the oxygen conversion of the hydro-oxidation catalyst that obtains reaches more than 99%, and the arene oxidizing selectivity is reduced to about 0.1%.Obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 0.536 gram chloroplatinic acid, 0.347 gram stannic chloride, 2.532 gram cerous nitrates and 0.926 gram lithium nitrate are dissolved in 40 ml deionized water and are mixed with dipping solution; With 100 gram pore volumes is the cylindric α-Al of 0.4 milliliter/gram, 4 millimeters of diameters, 5 millimeters of length
2O
3Carrier is put into rotatable container, adds dipping solution, keeps the internal tank temperature at 70～80 ℃, and rolling limit, limit dipping is up to the dipping solution complete obiteration; Baking oven was put in taking-up, 80 ℃ air dryings 4 hours; Roaster is put in taking-up, and roasting obtained the finished product hydro-oxidation catalyst in 4 hours in 550 ℃ air.
[embodiment 2]
Method according to embodiment 1 prepares catalyst, and different is that active precursor adopts 0.027 gram chloroplatinic acid, 0.035 gram stannic chloride, 0.253 gram cerous nitrate and 0.046 gram lithium nitrate.
[embodiment 3]
Method according to embodiment 1 prepares catalyst, and different is that active precursor adopts 0.536 gram chloroplatinic acid, 0.868 gram stannic chloride, 25.316 gram cerous nitrates and 4.631 gram lithium nitrates.
[embodiment 4]
Method according to embodiment 1 prepares catalyst, the spherical cyanines green stone that different is carrier adopts 100 gram pore volumes are 0.3 milliliter/gram, diameter are 4.5 millimeters; Active precursor adopts 2.684 gram chloroplatinic acids, 3.467 gram stannic chlorides, and 1.265 gram cerous nitrates and 0.926 gram lithium nitrate are dissolved in 30 ml deionized water and are mixed with maceration extract.
[embodiment 5]
Method according to embodiment 1 prepares catalyst, and different is that active precursor adopts 0.536 gram chloroplatinic acid, 0.868 gram stannic chloride, 2.52 gram lanthanum nitrates and 0.552 gram sodium nitrate.
The catalytic component composition of embodiment 1～5 sees Table 2, and normal pressure isotherm formula fixed bed evaluation result sees Table 3.
[embodiment 6]
Ethylbenzene dehydrogenation-hydroxide reaction carries out in negative pressure heat-insulating fixed bed reaction system, and the summary process is as follows:
With material ethylbenzene and deionized water preheating in measuring pump input preheater respectively, enter first reactor after the preheating and carry out ethylbenzene dehydrogenation reaction; Reacted material enters blender, mixes with the oxygen for preparing feeding, water vapour; Enter second reactor after the mixing and carry out the oxidation reaction of hydrogen; Reacted material enters the 3rd reactor again and carries out the dehydrogenation reaction second time.Reacted product is analyzed the composition of liquid phase with gas chromatograph after condensation, gas-liquid separation.Reactor is the stainless steel tube of 50 millimeters of internal diameters, the first and the 3rd reactor loads 750 milliliters of dehydrogenations respectively, this dehydrogenation is a dehydrogenation for the iron-potassium-cerium-molybdenum by patent ZL98110740.0 preparation, and second reactor loads 150 milliliters of hydro-oxidation catalysts of pressing embodiment 1 preparation.Evaluation result sees Table 4.
The evaluating catalyst condition is as follows in the negative pressure heat-insulating fixed bed reactors: first, second, third reactor inlet temperature is respectively 615 ℃, 540 ℃, 620 ℃; The 3rd reactor outlet pressure is absolute pressure 50KPa; Dehydrogenation part ethylbenzene liquid air speed is 0.45 hour
-1The weight ratio of water and ethylbenzene is 1.3.
Related conversion of ethylbenzene and selectivity of styrene computing formula are as follows:
The styrene list is received %=conversion of ethylbenzene * selectivity of styrene * 100%
[comparative example 1]
Method according to embodiment 1 prepares catalyst, and different is to adopt 0.536 gram chloroplatinic acid, 0.347 gram stannic chloride and 0.926 gram lithium nitrate.
[comparative example 2]
With 0.536 gram chloroplatinic acid, 0.347 gram stannic chloride and 0.926 gram lithium nitrate are dissolved in respectively and are mixed with three parts of dipping solutions in 20 ml deionized water; With 100 gram pore volumes is the cylindric α-Al of 0.4 milliliter/gram, 4 millimeters of diameters, 5 millimeters of length
2O
3Carrier is put into rotatable container, adds the stannic chloride dipping solution earlier, keeps the internal tank temperature at 70～80 ℃, and rolling limit, limit dipping is up to the dipping solution complete obiteration; Be sequentially added into chloroplatinic acid maceration extract and lithium nitrate maceration extract again, adopt the dipping that uses the same method and finish.Baking oven was put in taking-up, 80 ℃ air dryings 4 hours; Roaster is put in taking-up, and roasting obtained the finished product hydro-oxidation catalyst in 4 hours in 550 ℃ air.
The catalytic component composition of comparative example 1～2 sees Table 2, and normal pressure isotherm formula fixed bed evaluation result sees Table 2.
[comparative example 3]
According to the method evaluate catalysts of embodiment 6, different is not load hydro-oxidation catalyst in second reactor, only with 150 milliliters of filler fillings that reaction are inertia.Evaluation result sees Table 4.
Active component weight percentage in table 2 catalyst
| The percetage by weight % of active component in the catalyst | ||||
| Metal platinum | Tin oxide | Rare earth oxide | Alkali metal oxide | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 comparative example 2 | 0.201 0.010 0.201 1.007 0.201 0.201 0.201 | 0.200 0.020 0.501 2.000 0.501 0.200 0.200 | 1.000 10.000 0.100 0.500 1.001 - - | 0.200 0.010 1.000 0.200 0.201 0.200 0.200 |
Table 3 normal pressure isotherm formula fixed bed hydroxide reaction evaluation result
| Catalyst | Oxygen conversion % | Arene oxidizing selectivity % |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 comparative example 2 | 100 99.0 99.6 99.2 99.5 98.2 92.5 | 0.08 0.08 0.06 0.09 0.07 0.25 0.16 |
Table 4 negative pressure heat-insulating fixed bed ethylbenzene dehydrogenation-hydroxide reaction evaluation result
| Catalyst | Conversion of ethylbenzene % | Selectivity of styrene % | Styrene once through yield % |
| Embodiment 6 comparative examples 5 | 76.6 67.4 | 96.8 96.1 | 74.15 64.81 |
Claims (9)
1, a kind of catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction comprises following component by weight percentage:
(a) 0.01～1% platinum;
(b) oxide of 0.01～2% tin;
(c) oxide of 0.1～10% rare earth element;
(d) 88～99% to being reacted into the carrier of inertia.
2,, it is characterized in that the consumption of platinum is 0.05～0.3% by weight percentage according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 1; The oxide consumption of tin is 0.05～1%; The oxide consumption of rare earth element is 0.5～5%.
3,, it is characterized in that the consumption of platinum is 0.08～0.2% by weight percentage according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 2; The oxide consumption of tin is 0.1～0.5%; The oxide consumption of rare earth element is 1～2%.
4, according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 1, the carrier that it is characterized in that inertia is selected from least a in Alpha-alumina, silica, cyanines green stone, mullite or the spinelle.
5,, it is characterized in that the carrier of inertia is selected from Alpha-alumina or cyanines green stone according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 4.
6,, it is characterized in that by weight percentage also containing 0.01～1% in the catalyst is selected from alkali-metal oxide according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 1.
7,, it is characterized in that alkali metal is selected from lithium or sodium according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 6.
8,, it is characterized in that alkali-metal by weight percentage oxide consumption is 0.05～0.5% according to the described catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction of claim 6.
9, the described according to Claim 8 catalyst that is used for ethylbenzene dehydrogenation-hydroxide reaction is characterized in that alkali-metal by weight percentage oxide consumption is 0.2～0.4%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588008A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
| CN105622318A (en) * | 2014-11-20 | 2016-06-01 | 中国石油化工股份有限公司 | Heterotype potassium retarder used for ethylbenzene dehydrogenation-hydrogen oxidation reaction |
| CN107913719A (en) * | 2017-12-06 | 2018-04-17 | 江苏安琪尔废气净化有限公司 | Catalyst and preparation method for the noble metal low-load amount of VOCs catalysis burnings |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4914249A (en) * | 1988-12-29 | 1990-04-03 | Uop | Dehydrogenation of dehydrogenatable hydrocarbons |
| CN1204098C (en) * | 2002-03-13 | 2005-06-01 | 中国石油化工股份有限公司 | Oxide catalyst for ethylbenzene dehydrogenation to prepare styrene |
| CN1263541C (en) * | 2003-09-03 | 2006-07-12 | 中国石油化工股份有限公司 | Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene |
-
2005
- 2005-09-07 CN CNB2005100294608A patent/CN100408167C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588008A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
| CN104588008B (en) * | 2013-11-01 | 2017-03-01 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
| CN105622318A (en) * | 2014-11-20 | 2016-06-01 | 中国石油化工股份有限公司 | Heterotype potassium retarder used for ethylbenzene dehydrogenation-hydrogen oxidation reaction |
| CN107913719A (en) * | 2017-12-06 | 2018-04-17 | 江苏安琪尔废气净化有限公司 | Catalyst and preparation method for the noble metal low-load amount of VOCs catalysis burnings |
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