CN1927455A - Method for preparing thin shell hydroxide catalyst - Google Patents
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- CN1927455A CN1927455A CNA2005100294595A CN200510029459A CN1927455A CN 1927455 A CN1927455 A CN 1927455A CN A2005100294595 A CNA2005100294595 A CN A2005100294595A CN 200510029459 A CN200510029459 A CN 200510029459A CN 1927455 A CN1927455 A CN 1927455A
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Abstract
The invention relates to a method for preparing surface thin-case catalyst used in ethylbenzene dehydrogenation-hydroxide reaction. Wherein, it uses the IA group alkali metal hydroxide solution as deposit agent to pretreat at least one carrier of alpha- alumina, earth silicon, blue stone, mullite or spinel; then uses Pt-tin complex compound solution as emerge solution to emerge the treated carrier; then heating the catalyst complex compound in water at 150-550Deg. C; and baking it under 400-700Deg. C.
Description
Technical field
The present invention relates to a kind of preparation method of thin shell hydroxide catalyst.
Background technology
Styrene is important basic organic, is mainly used in to produce PS, ABS, materials such as SBR, SMA.At present, cinnamic in the world production method mainly is the ethylbenzene catalytic dehydrogenation method, 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.Uop Inc. of the U.S. utilizes the reaction mechanism of ethylbenzene dehydrogenation, has developed a kind of new technology of ethylbenzene dehydrogenation-hydroxide, i.e. SMART technology.In course of reaction, add oxygen, make the hydrogen of one of dehydrogenation product that oxidation reaction partly take place, break original chemical balance, it is moved to helping generating cinnamic direction, emit a large amount of heat simultaneously, provide a part of dehydrogenation reaction required heat, reduced energy consumption.One of key of this technology is a hydro-oxidation catalyst, for fear of oxygen penetration oxidation catalyst bed, and the too much oxidational losses of avoiding aromatic hydrocarbons, 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.This just needs active component in the catalyst must be in the state of high degree of dispersion, and the crystallite dimension of promptly main active component is as much as possible little.Patent US5043500 has introduced ethylbenzene dehydrogenation-hydroxide technology, and the hydroxide reaction catalyst system therefor in this process is to be main active component with precious metals pt, Pd, adds the oxide of Sn, Li, is carried on Al
2O
3On the carrier.
In hydroxide reaction, because the thermal discharge of reaction own is bigger, make easily load on the catalyst high degree of dispersion active component noble metal platinum generation crystal grain reunion and cause catalysqt deactivation, add the effect that tin oxide can play obstruction on the one hand to the reunion of platinum, on the other hand platinum had the electronic effect of drawing, weaken the strong suction-operated of platinum, therefore should closely combine at active site place platinum and tin oxide to hydrogen and oxygen.And noble metal isoreactivity component is carried in the very thin shell of carrier outer surface, impel reaction only to carry out at outer surface, the reaction liberated heat is shifted rapidly, fully, guaranteed noble metal catalyst long-term stability at high temperature.Patent US4914249, US5001291 and US5872075 etc. have introduced the composition and the preparation method of hydro-oxidation catalyst, mainly are the methods that adopts dipping.This method is simple, convenient, distributes but two kinds of main active component platinum and tin oxide are difficult to control it, make inhibition that tin oxide reunites to platinum a little less than.Therefore the characteristics of this class catalyst are high activity, high selectivity, but stability is relatively low, and high temperature easily takes place noble metal reunites.
The method for preparing the shell distribution of active component surface also has many.
In EP-0576944A1, the made non-porous material of a kind of mould of being made by materials such as glass, pottery, titanium dioxide, zirconium dioxide, aluminium oxide, alumina silicate, metal and graphite or their mixture has been described as carrier, preferred one or more oxidized easily metals and noble metal form alloy, method with physical vapor deposition or chemical vapour desposition makes alloy deposition on mechanograph, and the thickness of alloy-layer is 100nm～50 μ m.In DE-3200483A1, described that soluble and insoluble silica is applied on the base material of inorganic matter, the carrier that the mechanograph that makes can be used as various catalysis materials uses.In EP-0755718A1, the aqueous solution of having described the high dilution of at least a metallic compound is applied on the mechanograph of heat, water is evaporated immediately, and optionally calcining then is by so wear-resisting metal and metal oxide of covering on the non-porous inorganic carrier material that operate in.More than each method all be the technology that has adopted mechanograph, preparation were established is longer, control step complexity.
In DE-3037047C2, described with the carborundum of palladium salt solution impregnation as carrier, dry then and use hydrogen reducing.In US4812597, tin is flooded in a kind of elder generation on carrier saline solution has been described, and then the solution of platinum-impregnated, make platinum form shelly at carrier surface.In CN-1221653A, the suspension of having described at least a water-soluble precious metal chemical complex and a kind of water-fast substantially coating compound is dried on the surfaces of carrier materials, will activate then again.Above method mainly is that cost is higher, and perhaps the thickness of active shell is single, is difficult for regulating.
Summary of the invention
Technical problem to be solved by this invention is in preparation hydro-oxidation catalyst process, the active shell thickness of catalyst outer surface is difficult to control, active component is problem pockety in shell, and a kind of preparation method of novel thin shell hydroxide catalyst is provided.The catalyst that this method makes has active component and is evenly distributed in carrier outer surface shell, and the thickness of this shell layer can regulate within the specific limits, and in real reaction the advantage of good stability.
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 preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction may further comprise the steps:
(a) will be selected from least a carrier in Alpha-alumina, silica, cyanines green stone, mullite or the spinelle, with the hydroxide that is selected from IA family alkali metal, concentration is that the precipitating reagent of the aqueous solution of 0.01～5 mol carries out preliminary treatment;
(b) pretreated carrier is flooded with the complex solution that the compound of the compound of platinum and tin forms, the volume ratio of carrier total hole volume and complex solution is 1: 0.5～4 in the catalyst precarsor of formation;
(c) after the catalyst precarsor drying was handled, in the hydrothermal treatment consists of carrying out under 150～550 ℃ under water vapour and the air conditions, the water vapour of feeding and the volume ratio of air were 1: 0.1～10, and the processing time is 0.5～10 hour;
(d) catalyst precarsor is after hydrothermal treatment consists, and roasting obtained finished catalyst in 0.5～24 hour in 400～700 ℃ air.
In the technique scheme, the concentration preferable range of IA family alkali metal hydroxide aqueous solution is 0.1～1 mol.IA family alkali metal preferred version is for being selected from sodium or potassium.In the complex compound of used platinum tin, the atomic ratio preferable range of platinum tin is 1: 0.5～10, and more preferably scope is 1: 1～4.Complex compound with this platinum tin atom ratio can be dissolved in inorganic or the organic solvent, and the preferred version solvent is ethanol or hydrochloric acid.The temperature preferable range of hydrothermal treatment consists is 250～500 ℃, and the volume ratio preferable range of the water vapour of feeding and air is 1: 0.5～4, and the processing time preferable range is 2～6 hours.The sintering temperature preferable range is 450～600 ℃, and the roasting time preferable range is 1～4 hour.
The reaction that ethylbenzene dehydrogenation-hydroxide catalyst of the present invention is adapted to is the hydroxide reaction in the ethylbenzene dehydrogenation process, and the temperature range of reaction is 500～700 ℃, and the pressure limit of reaction is absolute pressure 0.1～10 standard atmospheric pressure; The reaction atmosphere that is adapted to is the mist of dehydrogenated tail gas, water vapour through producing after the ethylbenzene dehydrogenation and the oxygen that adds, nitrogen or air etc. before oxidation reaction.
The catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed, for hydro-oxidation catalyst performance evaluation, the summary process is as follows:
With raw material aromatic hydrocarbons mixture and deionized water preheating in measuring pump input preheater respectively, enter blender after the preheating, after the oxygen for preparing, nitrogen fully mix, enter reactor.Oxidation reactor adopts the heating wire heating, remains under the reaction temperature stable.Reactor is the stainless steel tube of 25 millimeters of internal diameters, loads the cylindric hydro-oxidation catalyst of 4.0 * 5.0 millimeters of 30 milliliters of .The product water condensation that flows out by reactor, after gas-liquid separation with gas chromatograph analysis composition separately.The oxidation catalyst appreciation condition is as follows in the isotherm formula fixed bed reactors: reaction pressure is a normal pressure, and the liquid air speed is 1.0 hours
-1, reaction temperature is 580 ℃.The raw material composition that enters oxidation reactor sees Table 1.
Oxygen conversion involved in the present invention and aromatic hydrocarbons combustion selective computing formula are as follows:
Table 1 hydroxide reaction aromatic hydrocarbons mixture raw material and phase feed are formed
| The hydroxide reaction raw material | Molar content % |
| Benzene toluene ethylbenzene styrene water hydrogen and oxygen nitrogen | 0.07 0.15 6.12 2.45 87.03 2.79 1.29 0.11 |
The present invention is owing to adopted the method for complex compound sediment to prepare thin shell hydroxide catalyst, overcome in the past thin-shell type catalyst preparation process complexity, preparation cost is higher, and the shortcoming that repeatability is bad, the thin shell hydroxide catalyst outer casing thickness that obtains is thin, and its average thickness only is below 0.1 millimeter; Main active component platinum crystallite dimension is little, and 1～20 nanometer is only arranged; Good stability in hydroxide reaction still remains on 97～99% through 500 hours operation oxygen conversion, and the aromatic hydrocarbons combustion selective still remains on below 0.2%.Obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
0.406 gram sodium chloroplatinite and 0.388 gram stannous chloride are mixed with platinum tin complex dipping solution after with 40 milliliters of anhydrous alcohol solutions.0.8 gram dissolution of sodium hydroxide is made into precipitant solution in 40 ml deionized water.With 100 4 millimeters of diameters of gram, 5 millimeters of length, pore volume is the α-Al of 0.4 milliliter/gram
2O
3Carrier is placed in the rotatable container, adds precipitant solution, and the dipping that rolls is until the precipitant solution complete obiteration, add the platinum tin complex dipping solution for preparing, keep the internal tank temperature at 65～75 ℃, rolling limit, limit dipping is up to the dipping solution complete obiteration.Take out the good catalyst precarsor of dipping 100 ℃ dry 2 hours down, put into internal diameter then and be 25 millimeters nonmetallic vessel, feeding temperature is 400 ℃, and flow is that the air that 120 liters/hour water vapour and flow are 240 liters/hour carries out hydrothermal treatment consists, and the time is 2 hours.The catalyst precarsor that takes out 550 ℃ of following roastings 4 hours, obtains the finished product hydro-oxidation catalyst in muffle furnace.Finished catalyst is through 480 ℃, 20 ml/min hydrogen reducings 2 hours, by transmission electron microscope observation Pt crystallite dimension, and optical microscope measuring active component shell layer thickness.
[embodiment 2]
Method according to embodiment 1 prepares catalyst, and different is is mixed with platinum tin complex dipping solution with 0.406 gram sodium chloroplatinite and 0.097 gram stannous chloride after with 20 milliliters of anhydrous alcohol solutions.0.016 gram dissolution of sodium hydroxide is made into precipitant solution in 40 ml deionized water.The temperature of hydrothermal treatment consists is 150 ℃, and steam rates is 600 liters/hour, and air mass flow is 60 liters/hour, and the time is 10 hours.The temperature of roasting is 400 ℃, and the time is 24 hours.
[embodiment 3]
Method according to embodiment 1 prepares catalyst, and different is is mixed with platinum tin complex dipping solution with 0.406 gram sodium chloroplatinite and 1.94 gram stannous chlorides after with 160 milliliters of anhydrous alcohol solutions.8 gram dissolution of sodium hydroxide are made into precipitant solution in 40 ml deionized water.The temperature of hydrothermal treatment consists is 400 ℃, and steam rates is 120 liters/hour, and air mass flow is 240 liters/hour, and the time is 2 hours.The temperature of roasting is 650 ℃, and the time is 0.5 hour.
[embodiment 4]
Method according to embodiment 1 prepares catalyst, and different is is mixed with platinum tin complex dipping solution with 0.406 gram sodium chloroplatinite and 0.388 gram stannous chloride after with 40 milliliters of anhydrous alcohol solutions.1.12 gram potassium hydroxide are dissolved in 40 ml deionized water and are made into precipitant solution.The temperature of hydrothermal treatment consists is 150 ℃, and steam rates is 60 liters/hour, and air mass flow is 600 liters/hour, and the time is 0.5 hour.The temperature of roasting is 400 ℃, and the time is 4 hours.
[embodiment 5]
Method according to embodiment 1 prepares catalyst, and different is to be mixed with platinum tin complex dipping solution after 0.274 gram platinous chloride and 1.94 is restrained the dissolving with hydrochloric acid that stannous chlorides are 3 mol with 20 ml concns.11.2 gram potassium hydroxide are dissolved in 40 ml deionized water and are made into precipitant solution.The temperature of hydrothermal treatment consists is 400 ℃, and steam rates is 120 liters/hour, and air mass flow is 240 liters/hour, and the time is 2 hours.The temperature of roasting is 550 ℃, and the time is 0.5 hour.
[embodiment 6]
Method according to embodiment 1 prepares catalyst, and different is to be mixed with platinum tin complex dipping solution after 0.274 gram platinous chloride and 0.194 is restrained the dissolving with hydrochloric acid that stannous chloride is 3 mol with 40 ml concns.0.016 gram dissolution of sodium hydroxide is made into precipitant solution in 40 ml deionized water.The temperature of hydrothermal treatment consists is 550 ℃, and steam rates is 60 liters/hour, and air mass flow is 600 liters/hour, and the time is 0.5 hour.The temperature of roasting is 550 ℃, and the time is 4 hours.
[comparative example 1]
0.541 gram chloroplatinic acid and 0.533 is restrained stannic chloride to be dissolved in the hydrochloric acid that 40 ml concns are 3 mol and to make dipping solution.With dry 5 millimeters of 4 millimeters of diameters, length, the pore volume of 100 grams is the α-Al of 0.4 milliliter/gram
2O
3Carrier is placed in the rotatable container, adds dipping solution, and the dipping while rotating is up to the dipping solution complete obiteration.Take out the good catalyst precarsor of dipping 100 ℃ dry 2 hours down, and then put into muffle furnace, 550 ℃ of following roastings 4 hours, obtain the finished product hydro-oxidation catalyst.Finished catalyst is through 480 ℃, 20 ml/min hydrogen reducings 2 hours, by transmission electron microscope observation Pt crystallite dimension, and optical microscope measuring active component shell layer thickness.
[comparative example 2]
Method with comparative example 1 prepares catalyst, and different is that 0.406 gram sodium chloroplatinite and 0.388 gram stannous chloride are dissolved in respectively in 20 milliliters of ethanol.With dry 5 millimeters of 4 millimeters of diameters, length, the pore volume of 100 grams is the α-Al of 0.4 milliliter/gram
2O
3Carrier is placed in the rotatable container, adds the ethanolic solution of stannous chloride earlier, and the dipping while rotating is up to the solution complete obiteration; And then the ethanolic solution of adding sodium chloroplatinite, the dipping while rotating is up to the solution complete obiteration.
[comparative example 3]
Method with comparative example 1 prepares catalyst, and different is that 0.388 gram stannous chloride is dissolved in 40 ml deionized water, and 0.274 gram platinous chloride is dissolved in the hydrochloric acid that 20 ml concns are 3 mol.With dry 5 millimeters of 4 millimeters of diameters, length, the pore volume of 100 grams is the α-Al of 0.4 milliliter/gram
2O
3Carrier is placed in the rotatable container, adds the aqueous solution of stannous chloride, and the dipping while rotating is up to the solution complete obiteration; And then the hydrochloric acid solution of adding platinous chloride, the dipping while rotating is up to the solution complete obiteration.
The composition of above-mentioned catalyst sees Table 1.Catalyst activity shell layer thickness sees Table 2.The Pt grain size distribution sees Table 3.Catalyst reaction stability evaluation result sees Table 4.
Table 1 catalytic component percentage composition
| Active component weight percentage/% in the catalyst | Platinum in the catalyst/tin atom ratio | ||
| Metal platinum | Tin oxide | ||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative example 2 comparative examples 3 | 0.199 0.199 0.199 0.199 0.201 0.201 0.203 0.199 0.199 | 0.308 0.308 0.154 0.616 0.308 0.308 0.308 0.308 0.308 | 0.5 2 0.1 0.5 0.1 1 0.5 0.5 0.5 |
Table 2 catalyst activity shell layer thickness
| Catalyst activity shell layer thickness | |||
| Average thickness/millimeter | Maximum ga(u)ge/millimeter | Minimum thickness/millimeter | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative example 2 comparative examples 3 | 0.092 0.099 0.072 0.089 0.084 0.093 4.000 2.604 0.103 | 0.102 0.110 0.075 0.099 0.090 0.100 4.000 2.922 0.127 | 0.082 0.087 0.068 0.078 0.079 0.085 4.000 2.285 0.079 |
Table 3 Pt grain size distribution
| Pt crystal grain accounts for overall quantity percentage/% in each size section quantity | ||||||
| 1～10nm | 10～20nm | 20～30nm | 30～40nm | 40～50nm | ＞50nm | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative example 2 comparative examples 3 | 92 90 84 93 89 96 74 99 86 | 7 6 11 5 10 4 15 1 11 | 1 2 3 2 1 0 6 0 3 | 0 2 1 0 0 0 5 0 0 | 0 0 1 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 0 |
Table 4 catalyst reaction stability evaluation result
| Oxygen conversion/% | Aromatic hydrocarbons combustion selective/% | |||||
| Move 24 hours | Move 500 hours | Amplitude of variation | Move 24 hours | Move 500 hours | Amplitude of variation | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative example 2 comparative examples 3 | 100.0 99.8 98.2 100.0 99.1 100.0 96.5 100.0 100.0 | 99.9 99.6 97.9 99.4 98.7 99.9 75.2 85.3 88.1 | -0.1 -0.2 -0.3 -0.6 -0.4 -0.1 -21.3 -14.7 -11.9 | 0.08 0.09 0.12 0.09 0.10 0.07 0.31 0.15 0.22 | 0.08 0.08 0.14 0.11 0.15 0.08 0.41 0.57 0.45 | 0 -0.01 +0.02 +0.02 +0.05 +0.01 +0.10 +0.42 +0.23 |
Claims (9)
1, a kind of preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction may further comprise the steps:
(a) will be selected from least a carrier in Alpha-alumina, silica, cyanines green stone, mullite or the spinelle, with the hydroxide that is selected from IA family alkali metal, concentration is that the precipitating reagent of the aqueous solution of 0.01～5 mol carries out preliminary treatment;
(b) pretreated carrier is flooded with the complex solution that the compound of the compound of platinum and tin forms, the volume ratio of carrier total hole volume and complex solution is 1: 0.5～4 in the catalyst precarsor of formation;
(c) after the catalyst precarsor drying was handled, in the hydrothermal treatment consists of carrying out under 150～550 ℃ under water vapour and the air conditions, the water vapour of feeding and the volume ratio of air were 1: 0.1～10, and the processing time is 0.5～10 hour;
(d) catalyst precarsor is after hydrothermal treatment consists, and roasting obtained finished catalyst in 0.5～24 hour in 400～700 ℃ air.
2, according to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 1, the concentration that it is characterized in that IA family alkali metal hydroxide aqueous solution is 0.1～1 mol.
3,, it is characterized in that IA family alkali metal is selected from sodium or potassium according to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 1.
According to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 1, it is characterized in that in the complex compound of used platinum tin that 4, the atomic ratio of platinum tin is 1: 0.5～10.
5, according to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 4, the atomic ratio that it is characterized in that platinum tin is 1: 1～4.
6, according to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 1, the temperature that it is characterized in that hydrothermal treatment consists is 250～500 ℃, the water vapour that feeds and the volume ratio of air are 1: 0.5～4, and the processing time is 2～6 hours.
7, according to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 1, it is characterized in that sintering temperature is 450～600 ℃, roasting time is 1～4 hour.
8, according to the described preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction of claim 4, the complex compound that it is characterized in that platinum tin be dissolved in inorganic or organic solvent in.
9, the described according to Claim 8 preparation method who is used for the thin shell hydroxide catalyst of hydroxide reaction is characterized in that inorganic solvent is selected from hydrochloric acid; Organic solvent is selected from ethanol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283125A (en) * | 2016-09-30 | 2017-01-04 | 广东省稀有金属研究所 | Metal electro-deposition coated titanium electrode and preparation method thereof |
| CN106607021A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for isobutane dehydrogenation production of isobutylene |
| CN112839735A (en) * | 2018-10-19 | 2021-05-25 | 喜星触媒株式会社 | Preparation method of high-efficiency branched light hydrocarbon dehydrogenation catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4812597A (en) * | 1987-09-02 | 1989-03-14 | Uop Inc. | Dehydrogenation of dehydrogenatable hydrocarbons |
| US4914249A (en) * | 1988-12-29 | 1990-04-03 | Uop | Dehydrogenation of dehydrogenatable hydrocarbons |
| CN1088399C (en) * | 1998-02-25 | 2002-07-31 | 中国科学院大连化学物理研究所 | Anti-toxic catalyst for deoxidation in high concentration CD and its preparation |
-
2005
- 2005-09-07 CN CNB2005100294595A patent/CN100418623C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607021A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for isobutane dehydrogenation production of isobutylene |
| CN106607021B (en) * | 2015-10-22 | 2020-02-04 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane |
| CN106283125A (en) * | 2016-09-30 | 2017-01-04 | 广东省稀有金属研究所 | Metal electro-deposition coated titanium electrode and preparation method thereof |
| CN112839735A (en) * | 2018-10-19 | 2021-05-25 | 喜星触媒株式会社 | Preparation method of high-efficiency branched light hydrocarbon dehydrogenation catalyst |
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