CN101491759B - Catalyst for hydrogen selective catalytic combustion reaction in ethyl benzene dehydrogenation process - Google Patents

Catalyst for hydrogen selective catalytic combustion reaction in ethyl benzene dehydrogenation process Download PDF

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CN101491759B
CN101491759B CN200810032916XA CN200810032916A CN101491759B CN 101491759 B CN101491759 B CN 101491759B CN 200810032916X A CN200810032916X A CN 200810032916XA CN 200810032916 A CN200810032916 A CN 200810032916A CN 101491759 B CN101491759 B CN 101491759B
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catalyst
combustion reaction
hydrogen selective
dehydrogenation process
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李应成
卢立义
翁漪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst for hydrogen selective catalytic combustion reaction during ethylbenzene dehydrogenation, and mainly solves the problems of low selectivity of catalyzing and combusting hydrogen by catalysts in the prior art. By adopting the technical proposal that a carrier is loaded with a catalyst active component using at least one platinum series metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum, at least one dressing agent selected from alkali metals and alkaline-earth metals, and an assistant catalyst selected from one of IVA compounds and at least one of VB compounds; the catalyst solves the problems, and can be applied in the industrial production of the hydrogen selective catalytic combustion reaction in a process of producing phenyl alkene by ethylbenzene dehydrogenation.

Description

The catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction
Technical field
The present invention relates to a kind of catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction.
Background technology
Styrene is a kind of important basic Organic Chemicals, is widely used in to produce plastics, rubber and resin etc.Ethylbenzene catalytic dehydrogenation is to produce cinnamic main method.Ethylbenzene dehydrogenation generates styrene and hydrogen is an endothermic reaction, thereby the obviously reduction in course of reaction of the bed temperature of catalyst, thereby has caused the reduction of feed stock conversion.Improve reaction temperature and can improve the conversion per pass of ethylbenzene, but still be subjected to the restriction of thermodynamical equilibrium.And a kind of more efficiently method of control reaction temperature is an aerating oxygen or contain the gas-selectively catalytic combustion hydrogen of oxygen in reaction, thereby improves reaction temperature, impels balance to move, and then improves ethylbenzene dehydrogenation and generate cinnamic conversion ratio.
The selective catalyst combustion reaction that hydrogen in the styrene is produced in ethylbenzene dehydrogenation carries out on noble metal catalyst.This class catalyst has a lot, for example, has introduced PtSnLi/Al among patent US4812597 and the US4914249 2O 3Catalyst adopts Pt as major catalyst, and Sn is as co-catalyst, and Li or other alkali metal or alkaline-earth metal adopt α-Al as dressing agent 2O 3As carrier, its shortcoming is that the precious metals pt consumption is higher in the catalyst.Patent US6177381 and CN1479649A have reported the layered catalyst composition.This catalyst has for example coating gama-alumina for example of Alpha-alumina and an inorganic oxide of a kernel.On the skin equably load platinum metal such as platinum and co-catalyst such as tin, catalyst also contains a kind of dressing agent such as lithium.And for example patent US6858769 and CN1705510A have reported that a kind of is the hydrogen selective catalyst combustion reaction catalyst of carrier with the lithium aluminate.This catalyst is a kernel with the cordierite, is coating with the lithium aluminate, load platinum metal and modified metal on coating, for example, platinum and tin.
The catalyst of above-mentioned patent preparation all is that eggshell type distributes, and promptly active component concentrates on the surperficial thin-shell type on carrier top layer.Eggshell type distribution catalyst can significantly reduce the consumption of noble metal, improves the utilization rate of noble metal.Simultaneously, the catalyst that eggshell type distributes in many reactions also showed than the better activity of equally distributed catalyst, selectivity and life-span.In addition,, for the such exothermic reaction of hydrogen selective catalyst combustion, more help the transfer of reaction heat, with stability that keeps catalyst and the service life that prolongs catalyst because active component concentrates on the carrier top layer.But when the catalyst of this invention is used for hydrogen selective catalyst combustion, the selectivity of burning hydrogen is high not enough, causes oxygen partial combustion aromatic hydrocarbons, causes the loss of raw material and product aromatic hydrocarbons, particularly under the situation of resource, energy growing tension, reduce consumption of raw materials and just seem more important.
Summary of the invention
Technical problem to be solved by this invention is prior art not high enough problem of catalyst selectivity when carrying out hydrogen selective catalyst combustion in ethylbenzene dehydrogenation process, and a kind of new catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion is provided.When this catalyst is used for the combustion reaction of ethylbenzene dehydrogenation process hydrogen selective, have catalyst burning hydrogen selectivity height, raw material and the low advantage of product aromatic hydrocarbons loss late.
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 the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction, to be selected from least a in aluminium oxide, carborundum, mullite, mullite, spinelle, cordierite, alumino-silicate, spodumene, zirconia or the titanium dioxide is carrier, by weight percentage, catalyst comprises following component:
A) being selected from least a in ruthenium in the platinum metal, rhodium, palladium, osmium, iridium or the platinum compounds, is 0.005～1.0% of catalyst weight in the simple substance consumption;
B) being selected from IA, the IIA compound at least aly, is 0.01～10% of catalyst weight in the simple substance consumption;
C) being selected from germanium among the IVA, tin or the plumbous compound at least aly, is 0.01～10% of catalyst weight in the simple substance consumption;
D) being selected from the VB compounds of group at least aly, is 0.001～5% of catalyst weight in the simple substance consumption;
E) carrier of surplus.
In the technique scheme, the carrier preferred version is selected from α-Al 2O 3, θ-Al 2O 3, δ-Al 2O 3, γ-Al 2O 3, at least a in spinelle, mullite or the cordierite.Carrier can be made different shapes as required, and as cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but sphere is reasonable selection, and its diameter is preferably 1～5 millimeter, so that commercial Application.Also can as required carrier be made lamellar composite carrier,, improve the decentralization of noble metal catalyst so that the effective active layer of control catalyst concentrates in the top layer of catalyst granules active component.The platinum metal preferred version is 0.02～1.0% of catalyst weight for being selected from platinum or palladium in simple substance consumption preferable range.IA, IIA element preferred version are to be selected from least a among Li, K, Mg or the Ba, are 0.05～5.0% of catalyst weight in simple substance consumption preferable range.IVA element preferred version is selected from Sn, is 0.05～2.0% of catalyst weight in simple substance consumption preferable range.VB element preferred version is to be selected from least a among V or the Nb, is 0.01～1.0% of catalyst weight in simple substance consumption preferable range.The catalyst preferred version is that the component of catalyst is the distribution of shell shape, and the effective active layer thickness is 1～100 micron.
Preparation of catalysts method of the present invention is as follows:
Catalyst activity component such as platinum group metal, co-catalyst VB element, IVA family element and dressing agent IA, IIA element can be dispersed on the carrier with any method that is suitable for obtaining surface impregnation.When preparation catalyst of the present invention, can use any decomposable platinum family compound, as halide, nitrate, oxide etc.: for example chloroplatinic acid, bromoplatinic acid, platinous chloride, platinum tetrachloride, ammonium chloroplatinate, sodium chloroplatinite, potassium chloroplatinite, dichloro four ammino platinum, dinitroso diammonia platinum, potassium chloroplatinate.Platinum-group component and dressing agent Li, K, Mg or Ba component can combine with carrier with random order.Can on carrier surface, flood platinum-group component earlier, follow one or more dressing agent components of surface impregnation again, also can flood one or more dressing agent components at carrier surface earlier, then flood platinum-group component; Certainly flood platinum-group component simultaneously and the dressing agent component also can.The IVA co-catalyst is comparatively suitable with stannous chloride and butter of tin; VB family co-catalyst there is no special restriction to its source, and is comparatively suitable with nitrate, oxalates, ammonium salt or chloride.Co-catalyst can load on earlier on the carrier, also can carry out surface impregnation again after the Pt load.Comparatively Chang Yong method is first load IVA, VB family co-catalyst, after dry and roasting, adopts the surface impregnation technology to flood to contain the solution of platinum and alkali metal, alkaline earth metal compound.At last, the catalyst precursor that will contain active component is earlier 100～150 ℃ of dryings 1～24 hour, then 200～700 ℃ of roastings 1～24 hour, under hydrogen or other reducing atmospheres, in 300～800 ℃ of reduction 1～4 hour, promptly make the catalyst that is used for hydrogen selective catalyst combustion reaction.
The oxygen conversion of indication of the present invention and oxygen selectivity obtain by following account form.
Figure GSB00000222718500031
Aromatic hydrocarbons loss late=1/8 (CO 2 (outlets)*+CO (outlet)÷ 22400 ÷ aromatic hydrocarbons (inlet)* 100%
Catalyst of the present invention is based on theory of thin shell, and the effective active layer by the control catalyst concentrates in the top layer of catalyst granules noble metal, presents the eggshell state structure of high dispersive, this class formation 2H that is highly advantageous to 2+ O 2→ 2H 2The O chemical reaction carries out, units activity component effective rate of utilization height, and catalyst has higher combustion activity, can bring into play the catalytic action of reactive metal Pt expeditiously.Each component synergy of catalyst makes the catalyst that makes have good hydrogen catalytic combustion selectivity simultaneously, is used for hydrogen selective catalyst combustion reaction, has the high remarkable advantage of burning hydrogen selectivity of catalyst.The selectivity that oxygen and hydrogen react is greater than 94%, and the aromatic hydrocarbons loss late has obtained better technical effect less than 0.2%.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 40 gram concentration is that glycerite, the 0.5 gram sorbester p17 of 15% alumina sol, 60 grams 2% made slurries.In this mixed liquor, add 0.5 gram potassic feldspar, 40 gram particle degree then at the γ-Al below 20 microns 2O 3Powder (200 meters of specific areas 2/ gram).Stir about adds 4.0 gram Ba (MO after ten minutes 3) 2And the SnCl of 1.5 grams 50% 4The aqueous solution, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.Slurries spray to the MgAl of 4 millimeters of particle diameters 2O 4On the bead, in 80 ℃ of dryings 2 hours, then be warming up to 100 ℃ dry 2 hours once more, in 1100 ℃ of roastings 6 hours, obtain lamellar composite carrier at last, consist of 13% (δ-Al 2O 3+ θ-Al 2O 3)/87%MgAl 2O 4ESEM shows about 90 microns of its coating layer thickness, and the coating specific area is 165 meters 2/ gram.
Niobium oxalate is dissolved in the water, is heated to 80 ℃, be immersed on the lamellar composite carrier of having made, then in 150 ℃ of dryings 2 hours.Again chloroplatinic acid is dissolved in the water, making its pH value with the HCl regulator solution is about 4, then this solution is heated to 80 ℃, is immersed on the lamellar composite carrier of having made, then in 150 ℃ of dryings 2 hours, then reductase 12 hour in 550 ℃ of hydrogen atmospheres, 650 ℃ are adopted the feeding water vapour then, do not have chlorion in tail gas, then are cooled to room temperature in air atmosphere, obtain catalyst A, composition sees Table 2.The component radial distribution of catalyst adopts EDX to measure 60 microns of effective active layer thicknesses.
[embodiment 2]
Niobium oxalate is dissolved in the water, is heated to 80 ℃, the vacuum rotary dipping 4 millimeters-Al 2O 3On the bead, then in 150 ℃ of dryings 2 hours.With SnCl 2, potassium chloride, magnesium chloride and chloroplatinic acid be dissolved in the water respectively, making its pH value with the HCl regulator solution is about 3, then this solution is heated to 75 ℃, be immersed in 4 millimeters-Al 2O 3On the bead, then in 150 ℃ of dryings 2 hours, then reductase 12 hour in 600 ℃ of hydrogen atmospheres obtains catalyst B, forms to see Table 2.The component radial distribution of catalyst adopts EDX to measure 80 microns of effective active layer thicknesses.
[embodiment 3]
Cyclodextrin solution, 2.0 gram ammonium metavanadates, the 1.0 gram softex kws of 35 gram alumina sols (aluminium oxide that contains 25% mass ratio), 5 grams, 40% Ludox, 60 grams 4% are made slurries.In this mixed liquor, add 0.4 gram calcium silicates, 0.3 gram potash and 40 gram particles then and directly be the δ-Al below 20 microns 2O 3Powder.Stir about adds the SnCl of 2.0 grams 50% after ten minutes 4The aqueous solution, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.Slurries spray on the mullite bead of 4 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 900 ℃ of roastings 6 hours, obtain lamellar composite carrier at last, consist of 16% (γ-Al 2O 3+ δ-Al 2O 3)/84% mullite.ESEM shows about 100 microns of its coating layer thickness, and the coating specific area is 152 meters 2/ gram.
Lithium nitrate and sodium chloroplatinite are dissolved in the water respectively, be mixed with mixed solution, making its pH value with the HCl regulator solution is about 4, then this solution is heated to 80 ℃, is immersed on the lamellar composite carrier of having made, then in 150 ℃ of dryings 2 hours, then 550 ℃ of roastings 2 hours, reductase 12 hour in 750 ℃ of hydrogen atmospheres obtains catalyst C, forms to see Table 2.The component radial distribution of catalyst adopts EDX to measure 84 microns of effective active layer thicknesses.
[embodiment 4]
Ammonium metavanadate, potassium nitrate are dissolved in the water respectively, vacuum impregnation on cordierite carrier, 150 ℃ of dryings 2 hours.With SnCl 4And sodium chloroplatinite is dissolved in the ethanolic solution, be immersed on the carrier once more, 150 ℃ of dryings 2 hours, then reductase 12 hour in 550 ℃ of hydrogen atmospheres, 650 ℃ are adopted the feeding water vapour then, do not have chlorion in tail gas, then are cooled to room temperature in air atmosphere, obtain catalyst D, composition sees Table 2.The component radial distribution of catalyst adopts EDX to measure 95 microns of effective active layer thicknesses.
[embodiment 5]
10 grams, 40～60 order magnesium aluminate spinel carriers are encased in the CVD reactor, the upper ends carrier, the lower end is placed and is fluoridized niobium powder.Reactor is the crystal reaction tube of 10 millimeters of internal diameters, 300 millimeters of length.Reactor is divided into two sections, and the centre is equipped with sintered glass respectively.Reactor adopts the external heating mode heating, and 2 parallel thermocouples are equipped with to control and to measure the heating-up temperature of hypomere on the reactor respectively in the outside.The reactor epimere is heated to 50 ℃ of temperature, at pressure 10 -6Vacuumized cool to room temperature under the torr 3 hours.Then heat the hypomere reactor with 5 ℃ of/minute clock rate of speed, and be warming up to 250 ℃, insulation is 10 hours under this temperature.Then be cooled to 150 ℃, under this temperature, feed steam, be incubated 5 hours once more, under nitrogen protection, be warming up to 600 ℃ of roastings 4 hours at last, obtain Nb 2O 5/ MgAl 2O 4Then with SnCl 4Solution impregnation in vacuum impregnation at Nb 2O 5/ MgAl 2O 4On, 150 ℃ of dryings 2 hours.Again lithium nitrate, the acid of chlorine palladium and platinum acid chloride solution are heated to 80 ℃, flooded above-mentioned carrier 10 minutes, 150 ℃ of dryings 2 hours, then 500 ℃ of roastings 4 hours, reductase 12 hour in 600 ℃ of hydrogen atmospheres obtains catalyst E, forms to see Table 2.The component radial distribution of catalyst adopts EDX to measure 100 microns of effective active layer thicknesses.
[comparative example 1]
The preparation of this oxidation catalyst is shown in the embodiment 2 of 4812597 li of the U.S. Pat mentioned in the reference of front.Elementary analysis shows with regard to whole catalyst and contains Pt 0.20% according to the mass fraction meter, and Sn 0.23%, and Li 0.20%.Catalyst is marked as F.The component radial distribution of catalyst adopts EDX to measure 150 microns of effective active layer thicknesses.
[comparative example 2]
The preparation of this oxidation catalyst is shown in the embodiment 3 of 6858769 li of the U.S. Pat mentioned in the reference of front.Elementary analysis shows with regard to whole catalyst and contains Pt 0.14% according to the mass fraction meter, and Sn 0.16%, and Li 0.72%.Catalyst is marked as G.The component radial distribution of catalyst adopts EDX to measure 120 microns of effective active layer thicknesses.
[embodiment 6]
Hydrogen selective catalyst combustion reaction carries out in internal diameter is 25 millimeters stainless steel reaction pipe, in adorn 30 milliliters of catalyst.Reaction pressure is a normal pressure, liquid air speed 3 hours -1, 580 ℃ of reaction temperatures, reactant is formed as table 1.
The raw material of H 2 selective oxidation is formed in table 1 ethylbenzene dehydrogenation process
Raw material Content (molar percentage)
Styrene 2.4
Ethylbenzene 5.4
Benzene and toluene 0.08
H 2 2.4
O 2 1.1
N 2 0.11
Water 88.51
The results are shown in Table 2 for activity of such catalysts and selectivity.As can be seen from the table, the catalyst O of this method preparation 2Selectivity all be higher than 94%, and the aromatic hydrocarbons loss late all is lower than 0.09%, reference catalyst O 2Selectivity all be lower than 93%, and the aromatic hydrocarbons loss late is 0.11%, has shown that catalyst of the present invention is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction, has higher hydrogen catalytic combustion selectivity and lower aromatic hydrocarbons loss late.
The composition of table 2 catalyst and reactivity worth

Claims (7)

1. catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction, to be selected from least a in aluminium oxide, carborundum, mullite, mullite, spinelle, cordierite, alumino-silicate, spodumene, zirconia or the titanium dioxide is carrier, by weight percentage, catalyst is made up of following component:
A) being selected from least a in ruthenium in the platinum metal, rhodium, palladium, osmium, iridium or the platinum compounds, is 0.005～1.0% of catalyst weight in the simple substance consumption;
B) being selected from IA, the IIA compound at least aly, is 0.01～10% of catalyst weight in the simple substance consumption;
C) being selected from germanium among the IVA, tin or the plumbous compound at least aly, is 0.01～10% of catalyst weight in the simple substance consumption;
D) being selected from the VB compounds of group at least aly, is 0.001～5% of catalyst weight in the simple substance consumption;
E) carrier of surplus.
2. according to the described catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction of claim 1, it is characterized in that carrier is selected from α-Al 2O 3, θ-Al 2O 3, δ-Al 2O 3, γ-Al 2O 3, at least a in spinelle, mullite or the cordierite.
3. according to the described catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction of claim 1, it is characterized in that platinum metal is selected from platinum or palladium, is 0.02～1.0% of catalyst weight in the simple substance consumption.
4. according to the described catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction of claim 1, it is characterized in that IA, IIA element are selected from least a among Li, K, Mg or the Ba, be 0.05～5.0% of catalyst weight in the simple substance consumption.
5. according to the described catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction of claim 1, it is characterized in that the IVA element is selected from Sn, is 0.05～2.0% of catalyst weight in the simple substance consumption.
6. according to the described catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction of claim 1, it is characterized in that the VB element is selected from least a among V or the Nb, be 0.01～1.0% of catalyst weight in the simple substance consumption.
7. according to the described catalyst that is used for the ethylbenzene dehydrogenation process hydrogen selective catalyst combustion reaction of claim 1, it is characterized in that the component of catalyst is the distribution of shell shape, the effective active layer thickness is 1～100 micron.
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CN102441378B (en) * 2010-10-13 2013-08-28 中国石油化工股份有限公司 Dehydrogenation catalyst for straight-chain paraffin and preparation method thereof
CN104549248B (en) * 2013-10-22 2017-02-08 中国石油化工股份有限公司 Preparation method for catalyst for dehydrogenation of low-carbon alkane
CN106732577B (en) * 2015-11-19 2019-09-10 中国石油化工股份有限公司 A kind of itrogenous organic substance catalyst for catalytic combustion and its preparation method and application
EA202090423A1 (en) * 2017-08-24 2020-06-04 Стар Сайентифик Лимитед COMPOSITIONS, METHODS AND DEVICES FOR CATALYTIC BURNING
DE102018109254A1 (en) * 2018-04-18 2019-10-24 Clariant lnternational Ltd Platinum-coated catalyst
CN112569917A (en) * 2019-09-27 2021-03-30 中国石油化工股份有限公司 Catalyst carrier, catalyst and method for producing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon

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