CN1033756A - Dehydrogenation catalyst and preparation method thereof and in the application for preparing with linear paraffinic hydrocarbons in the linear alpha-olefin - Google Patents
Dehydrogenation catalyst and preparation method thereof and in the application for preparing with linear paraffinic hydrocarbons in the linear alpha-olefin Download PDFInfo
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- CN1033756A CN1033756A CN88104700A CN88104700A CN1033756A CN 1033756 A CN1033756 A CN 1033756A CN 88104700 A CN88104700 A CN 88104700A CN 88104700 A CN88104700 A CN 88104700A CN 1033756 A CN1033756 A CN 1033756A
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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Abstract
Be used to make linear paraffinic hydrocarbons to be dehydrogenated to the catalyzer of linear alpha-olefin.This catalyzer comprises a kind of solid porous bead-type substrate that the water soluble salt of platinum, indium, thallium and a kind of basic metal or alkaline-earth metal is arranged.Weight ratio between some paired metal is critical.After the impregnated solid particles drying calcining, can be arbitrarily with hydrogen reducing or sulfuration.The catalyzer of making like this is efficiently with long-life.
Description
The present invention relates to a kind of dehydrogenation catalyst, it the preparation method and in the application for preparing with the linear paraffinic hydrocarbons dehydrogenation in the linear alpha-olefin.
The linear alpha-olefin of carbon atom quantity higher (for example 9 or higher) has purposes widely in technical field in the molecule.For instance, the linear alpha-olefin class that contains 12 carbon atoms (mean number) in the molecule is used to prepare the alkyl benzene with linear alkyl chain.They are valuable intermediates of producing biodegradable detergent.
Make the linear paraffinic hydrocarbons dehydrogenation prepare the method for linear alpha-olefin, technical is well-known, the air-flow that wherein hydrogen and linear paraffinic hydrocarbons are formed, high temperature be equal to or higher than atmospheric pressure under contact with dehydrogenation catalyst.
The catalyzer that is suitable for this purpose contains platinum or platinum metals usually, is carrier with silicon oxide, aluminum oxide, natural or synthetic silico-aluminate or the like.
Show at this catalyzer under the condition of dehydrogenation activity, many pairs of reactions are arranged, for example reactions such as the pyrolysis of alkane and/or alkene, isomerization and cyclisation take place.
In addition, also often there is excessive dehydrogenation reaction to take place, generates the degree of unsaturation product higher than monoolefine, for example, the alkadiene product.
The phenomenon of usually running in dehydrogenation reaction process at last, is that catalyst deactivation is quite fast.The inactivation of catalyzer is accompanied by usually and coking occurs, and the work-ing life of catalyzer is shortened in the coking meeting, and is an industrial heavy burden.
Activity and selectivity when being used for dehydrogenated operation in order to improve dehydrogenation catalyst, prior art once advised using carried catalyst, this catalyzer removes and contains platinum, or outside a kind of metal in the platinum family, also contain the element that one or more are selected from gallium, indium, scandium, yttrium, lanthanum, actinium, tin, basic metal or alkaline-earth metal etc., for example, resemble among US-A-2814559, US-A-2914464 and the US-A-3892657 disclosed.
Patent GB-B-1499297 has reported other catalyst composition, this patent disclosure a kind of be the catalyzer of carrier with the aluminum oxide, it contains platinum, a kind of basic metal and at least a element of selecting from gallium, indium, thallium.In addition, US-A-4486547 also discloses a kind of catalyzer of porous carrier, and this catalyzer contains a kind of platinum metals, tin, indium and a kind of basic metal or a kind of alkaline-earth metal, and strictly limits the ratio of indium and platinum metals.
Can improve activity and the selectivity of linear paraffinic hydrocarbons dehydrogenation with production of linear alkene though proved the various catalyst compositions that exemplify above, with regard to the hold-time of these valuable performances, be unsafty.
Therefore, an object of the present invention is to overcome these defectives of prior art.
Have been found that according to ultimate principle of the present invention, that is: be attached on the platiniferous carried catalyst by the indium and the thallium that will have accurate ratio each other, just can obtain to be used to the high reactivity and the high-selectivity catalyst that make linear paraffinic hydrocarbons be dehydrogenated to linear alpha-olefin.This catalyzer can also keep these performances constant for a long time.
So, an object of the present invention is to provide a kind of dehydrogenation catalyst, this dehydrogenation catalyst makes the linear paraffinic hydrocarbons dehydrogenation have activity and selectivity in production of linear alkene, and can keep this activity and selectivity for a long time.
Another object of the present invention provides a kind of method for preparing above mentioned the sort of catalyzer.
Another object of the present invention is to use these catalyzer in the process that is starting raw material production of linear alkene with the linear paraffinic hydrocarbons.
Other purpose of the present invention and feature thereof will be able in the narration of back clearly.
Therefore, the invention provides a kind of dehydrogenation catalyst, this dehydrogenation catalyst comprises a kind of solid-state, particulate porous property carrier, deposits on carrier: platinum total catalyst weight 0.1～1%(weight), 0.1～1%(weight) tin, 0.05～1%(weight) indium, 0.01～1%(weight) thallium, 0.05～3.5%(weight) be selected from a kind of metal in basic metal or the alkaline-earth metal.Above-mentioned percentage number average is the percentage ratio to total catalyst weight.Indium to the weight ratio of thallium between 0.3: 1 and 6: 1, platinum to the weight ratio of indium and thallium between 0.3: 1 and 1.5: 1.
In the catalyzer of the present invention, the weight ratio of platinum and tin should maintain between 0.5: 1～2: 1, and the weight ratio of platinum and basic metal or alkaline-earth metal should be determined on a case-by-case basis between 0.2: 1 and 2.5: 1.
Or rather, when selecting basic metal for use, platinum to the ratio of basic metal between 0.2: 1 to 2: 1 better, and when selecting alkaline-earth metal for use, platinum to alkaline-earth metal than between 0.1: 1 to 4: 1 for good.
In a typical embodiment, the total amount of the contained catalytic metal of catalyzer of the present invention is 1% to 3% of this total catalyst weight, in these catalytic metals, preferably indium is 1: 1 to 5: 1 to the variation range of the weight ratio of thallium, platinum is 0.8: 1 to 1: 1 to the variation range of the weight ratio of indium and thallium, platinum is 0.8: 1 to 1: 1 to the variation range of the weight ratio of tin, platinum is 0.3: 1 to 1.5: 1 to relevant alkali-metal weight ratio, for molecular weight lower basic metal or alkaline-earth metal, should select lower weight ratio.
Lithium is preferred basic metal.
Being suitable for the carrier that the present invention uses is high-specific surface area and high pore volume solid granulates shape carrier, and the specific surface area of this carrier is usually greater than 100 square metres/every gram (m
2/ g), pore volume is usually above the every gram milliliter of 0.5ml/g(number).This carrier is selected from silicon oxide, aluminum oxide, natural or synthetic silico-aluminate usually.
Carrier is γ-crystal formation aluminum oxide preferably, and its specific surface area is 100 to 400m
2Between/the g, total pore volume between 0.15 to 1.2mL/g, when being used for fixing bed bioreactor in pelletized form.
The first step for preparing this catalyzer is the acidic aqueous solution (particularly using this aqueous solution of nitric acid acidifying) with the compound of a kind of platinum, tin, indium and thallium: impregnated carrier.Say that more properly these metallic compounds are salt and acids, they are water miscible, but pyrolytic decomposition.
The example that is applicable to the compound of above-mentioned purpose has: Platinic chloride, tin chloride, indium nitrate and thallium trinitrate (TTN).
Appropriate dipping method is, is envrionment temperature (20～25 ℃) or near under the envrionment temperature constantly stirring carrier and service temperature, and the above-mentioned aqueous solution is added on the solid support material.
The adding of catalytic metal can add by the mode of single-steeping or by the mode in continuous impregnating cycle repeatedly.
After finishing dipping cycle or single-steeping step as the case may be, may need impregnated carrier is carried out drying treatment, especially when the total pore volume of volume ratio carrier of the solution of dipping usefulness is big, need make this drying treatment.The main purpose in this step is to remove the excessive solvent that is not adsorbed.
This drying step carries out under airflow to good, and drying temperature is between 100 ℃～130 ℃.
The carrier of handling according to the method described above then again with the aqueous solution dipping of alkali-metal oxyhydroxide, perhaps with the nitrate of alkaline-earth metal or the aqueous solution dipping of oxyhydroxide, is determined on a case-by-case basis.
In this case, the method for most convenient still adds above-mentioned solution under the situation that constantly stirs solid-state carrier, and this operation ties up to envrionment temperature (20～25 ℃) or near carrying out under the envrionment temperature.
After finishing the dipping second time, can carry out drying treatment under these conditions again, carry out calcination subsequently and handle.Calcination is handled and should be carried out under airflow, handles 2～8 hours under 450～550 ℃ of temperature.
An alternative concrete scheme of the method according to this invention the steps include: the solution impregnating carrier with the compound of a kind of platinum, tin, indium and thallium; The impregnated carrier of calcination (if desired, can in advance through super-dry); As the case may be, with the carrier of the aqueous solution dipping calcination of the nitrate of the aqueous solution of alkali metal hydroxide or alkaline-earth metal or oxyhydroxide; Again the catalyzer that makes is carried out drying treatment.
According to another embodiment, carrier is with following aqueous solution dipping.This aqueous solution indistinction ground comprises all catalytic metal compounds, in other words, except the compound of platinum, tin, indium and thallium, also includes alkali metal compound or alkaline earth metal compound.If like this after finishing this step of dipping, carry out drying, carry out calcination then and handle.
In any case, all must reduce by the catalyzer of method for preparing.The method that realizes reduction step is, under high temperature (350-500 ℃) and environmental stress or higher slightly pressure, makes catalyzer contact 2～20 hours with gaseous hydrogen.
With sulfuration reagent, as hydrogen sulfide, it is useful handling with the catalyzer after the reduction that obtains thus, and the sulfuration reagent dosage should make that sulphur in the catalyzer is about 2: 1 to the atomic ratio of platinum.
This last treatment step should carry out under the condition of dehydrogenation (promptly in 400～500 ℃ of scopes) being suitable for, and with reaction mixture, will deliver on the catalyzer after the reduction with the hydrogen sulfide air-flow behind the nitrogen dilution.
The final catalyzer that obtains thus makes linear paraffinic hydrocarbons be dehydrogenated to that existing high activity has high selectivity again in the process of linear alpha-olefin, and is keeping these performances not to be subjected to the influence of the runtime of unpredictable length.
Say that more properly the linear paraffinic hydrocarbons of carrying out dehydrogenation reaction is the linear paraffinic hydrocarbons that contains 9 or more carbon atoms (for example 9～20 carbon atoms) in those molecules, particularly contain the linear paraffinic hydrocarbons of 10～14 carbon atoms.
These paraffinic feedstocks be with gaseous form and hydrogen together (hydrogen is 1: 1 to 15: 1 to the mol ratio of alkane) be admitted in the fixed-bed reactor that catalyzer is housed, temperature of reaction is at 400～550 ℃, pressure preferably surpasses normal atmosphere (0.5 to 5Kg/cm
2) with respect to the HLSV(liquid hourly space velocity of liquid alkane flow rate calculation) be 5～100 o'clock
-1
Routinely linear alpha-olefin is separated from other products of dehydrogenation reactions at last.
The following examples 1-7 is used for illustrating embodiment of the present invention, has used alkali metal compound and other catalytic metal in these embodiments simultaneously; Embodiment 8 and 9 is comparative examples, and it makes and can compare with prior art.
Embodiment 9 and 10 is practical embodiment, is to be used for explanation: how to prepare catalyzer according to the present invention; The use properties of catalyzer in certain embodiments with comparative examples.
Embodiment 1
The carrier of catalyzer is commercially available gama-alumina, has following technical specification:
Surface-area 196m
2/ g
Total pore volume 0.75mL/g
Particle size 1.25～1.6mm
In this gama-alumina of 90g, under agitation slowly add 120mL by 0.09g thallium trinitrate (TTN) (I), 0.95g five nitric hydrate indiums, 0.9g tin chloride, the aqueous solution that 2.1g Platinic chloride (Pt of 16% weight) and 6g65% nitric acid are made.
Under envrionment temperature (20～25 ℃), continue to mix one hour, then mixture is heated to 120 ℃ in airflow, continue one hour, so that really fully evaporate excessive water solvent.
The dried solids that obtain thus are placed in the retort furnace, and under 500 ℃, calcination is 4 hours in airflow.
Preparation 120mL contains the aqueous solution of 1.7g lithium hydroxide.
At ambient temperature, above-mentioned solution is slowly added solids after the above-mentioned calcination of stirring.Envrionment temperature with continue to stir under continue contact 1 hour and in airflow under 120 ℃ lasting 1 hour again.
One finishes i.e. cooling, just can obtain a kind of catalyzer.See Table 1.
Embodiment 2
To in the commercially available gama-alumina of crossing described in the embodiment 1 of 90g, under agitation slowly add the aqueous solution that 120mL is made into by 0.33g thallium trinitrate (TTN) (I), 0.80g five nitric hydrate indiums, 1.0g tin chloride and 6g65% nitric acid.After under envrionment temperature (20～25 ℃) and continuously stirring, contacting 1 hour, this reactant is heated to 120 ℃ in air, and under this temperature, in airflow, kept 1 hour, really fully evaporate excessive water to impel.
Preparation 120mL contains the aqueous solution of 2.5g Platinic chloride (Pt that contains 16% weight) and 6g65% nitric acid.
At ambient temperature, this solution is slowly joined in the drying solid particle that is stirring.In envrionment temperature with under continue stirring, continue contact 1 hour, and in airflow 120 ℃ of following restir 1 hour.
Thus obtained dried solids are placed in the retort furnace, in airflow, heated 4 hours down at 500 ℃.
In time preparation 120mL contains the aqueous solution of 1.4g lithium hydroxide.
At ambient temperature, above-mentioned solution is slowly joined in the solids of the calcination of stirring.Envrionment temperature with continue to stir under make and continue to contact 1 hour, and in airflow, in 120 ℃ of following restir 1 hour.
One finishes aforesaid operations promptly cools off, and can obtain a kind of catalyzer, and its composition is listed in the table 1.
Embodiment 3
To at 90g in the gama-alumina of crossing described in the embodiment 1, under agitation slowly add the aqueous solution that 100mL is made by 2.6g Platinic chloride (Pt that contains 16% weight), 1.1g tin chloride, 6g65% nitric acid.After envrionment temperature (20～25 ℃) contacts 1 hour down, under continuously stirring, reactant is heated to 120 ℃ in air, and under this temperature, kept 1 hour, so that excessive water really fully evaporates.
Preparation 100mL contains the aqueous solution of 0.58g thallium trinitrate (TTN) (I), 0.83g five nitric hydrate indiums and 6g65% nitric acid.
At ambient temperature, above-mentioned solution is slowly joined in the solids that the drying that stirring crosses.
Continue contact 1 hour at ambient temperature, and in airflow, under 120 ℃, restir 1 hour.
In time preparation 100mL contains the aqueous solution of 1.8g lithium hydroxide.
At ambient temperature, above-mentioned solution is slowly joined in the solids that the drying that stirring crosses.Envrionment temperature with stir under continue to contact 1 hour, and in airflow, under 120 ℃, restir 1 hour.
With thus obtained solids in retort furnace, in airflow, in 500 ℃ of following calcination 4 hours.
One finishes aforesaid operations promptly cools off, and can obtain a kind of catalyzer, and its composition is listed in the table 1.
Embodiment 4
Adopt the operation steps the same, be used in the commercially available gama-alumina 90g that described among the embodiment 1 and add the following aqueous solution in succession to prepare catalyzer with embodiment 1:
A) aqueous solution made by 0.15g thallium trinitrate (TTN) (I), 0.34g five nitric hydrate indiums, 0.6g tin chloride, 1.1g Platinic chloride (Pt that contains 16% weight) and 4g65% nitric acid of 80mL;
B) 80mL contains the aqueous solution of 1.2g lithium hydroxide.
In retort furnace, under 500 ℃, calcination is 4 hours in airflow with the solids after flooding thus.Can obtain a kind of catalyzer thus, its composition is listed in the table 1.
Embodiment 5
In the commercially available gama-alumina of the 90g that in embodiment 1, described, in envrionment temperature (20～25 ℃) with under stirring, slowly add the aqueous solution that 67.5mL is made into by 0.13g thallium trinitrate (TTN) (I), 0.89g five nitric hydrate indiums, 1.9g Platinic chloride (Pt that contains 16% weight), 0.7g tin chloride and 4g65% nitric acid.
After reinforced,, and under this temperature, in airflow, kept 1 hour mixture heating up to 120 ℃.To impregnated solids thus, in retort furnace, under 500 ℃, calcination is 4 hours in airflow.
With 3.1g lithium hydroxide preparation cumulative volume is the 67.5mL aqueous solution.
Under envrionment temperature (20-25 ℃), above-mentioned solution is slowly joined in the solids after the calcination of stirring.After reinforced, in airflow, be heated to 120 ℃ and keep and carried out drying in 1 hour.
One finishes the i.e. cooling of these operations, can obtain a kind of catalyzer, and its composition is listed in the table 1.
Embodiment 6
Adopt embodiment 1 described operation steps again, be used in the commercially available gama-alumina 90g that described among the embodiment 1, add the following aqueous solution in succession to prepare catalyzer:
A) aqueous solution made by 2.4g Platinic chloride (Pt that contains 16% weight), 1.0g tin chloride and 6g65% nitric acid of 100mL;
B) aqueous solution made by 0.16g thallium trinitrate (TTN) (I), 1.1g five nitric hydrate indiums and 0.7g lithium hydroxide of 100mL.
In retort furnace, under 500 ℃, calcination is 4 hours in airflow, can obtain a kind of catalyzer thus with impregnated solids, and its composition is listed in the table 1.
Embodiment 7
In the commercially available gama-alumina of the 90g that in embodiment 1, described,, slowly add the aqueous solution that 67.5mL is made by 3.7g Platinic chloride (Pt that contains 16% weight), 1.2g tin chloride and 4g65% nitric acid in envrionment temperature (20-25 ℃) with under stirring.
Finish reinforced after, whole mixtures are heated to 120 ℃ in airflow, and under this temperature, kept 4 hours.
Preparation 67.5mL contains the aqueous solution of 0.23g thallium trinitrate (TTN) (I), 1.6g five nitric hydrate indiums and 2g65% nitric acid.
Under envrionment temperature (20～25 ℃), above-mentioned solution is slowly joined in the dried solids that stirring.After reinforced the finishing, in airflow, be heated to 120 ℃, dry 1 hour, then in retort furnace, under the airflow, 500 ℃ of calcination 4 hours.
With the 1.5g lithium hydroxide preparation 67.5mL aqueous solution.
Under envrionment temperature (20～25 ℃), above-mentioned solution is slowly joined in the solids after the calcination of stirring.
After above-mentioned reinforced the finishing, these solids are heated to 120 ℃ in airflow, carry out drying.
Can obtain a kind of catalyzer thus, its specification is as shown in table 1.
Embodiment 8(contrasts and uses)
Adopt embodiment 1 described operation steps, be used in the commercially available gama-alumina 90g that described among the embodiment 1, add the following aqueous solution in succession to prepare catalyzer:
A) aqueous solution made by 2.15g Platinic chloride (Pt that contains 16% weight), 0.7g thallium trinitrate (TTN) (I) and 6g65% nitric acid of 120mL;
B) 120mL contains the aqueous solution of 1.6g aluminium hydroxide.
With final product in retort furnace, under 500 ℃, in airflow, calcination 4 hours.
Can obtain a kind of catalyzer thus, its composition is listed in the table 1.
Embodiment 9(contrasts and uses)
Adopt the operation steps described in the embodiment 1, be used in the commercially available gama-alumina 90g that described among the embodiment 1, add the following aqueous solution in succession to prepare catalyzer by a given order:
A) aqueous solution made by 2.4g Platinic chloride (Pt that contains 16% weight), 0.95g tin chloride, 1.3g five nitric hydrate indiums and 6g65% nitric acid of 120mL;
B) 120mL contains the aqueous solution of 1.7g lithium hydroxide.
In retort furnace, under 500 ℃, calcination is 4 hours in airflow, can obtain a kind of catalyzer thus with final product, and its composition is as shown in table 1.
Embodiment 10
Use various catalyzer to carry out the test that the linear paraffinic hydrocarbons deoxidation prepares linear alpha-olefin according to embodiment 1 to embodiment 9 described method preparation., the various catalyzer of 8mL are contained in the fixed bed tubulose microreactor for this reason, and carry out prereduction in hydrogen stream, reduction temperature is 400 ℃, and pressure is 2Kg/cm
2, the reaction times is 15 hours.
Subsequently, various catalyzer are carried out sulfidizing, the required treatment time should be long enough to make S/Pt atomicity ratio near 2: 1.For reaching this purpose, should in being sent to the general dehydrogenation reaction mixture of catalyzer, replenish to contain the 5%(volume) gas mixture of hydrogen sulfide, the rest part of gas mixture is a nitrogen.Curing temperature is 460 ℃, and pressure is 2Kg/cm
2
Through after handling like this, begin formal dehydrogenation test, method is to contain C
10～C
13Linear paraffinic hydrocarbons, the gaseous mixture of hydrogen G﹠W join in the dehydrogenation reactor.Hydrogen is 5: 1 to the mol ratio of linear paraffinic hydrocarbons, and the mixture water content is 2000 heavy ppm(weight PPMs).
In addition, dehydrogenation reaction is to be that 465 ℃, pressure are 2Kg/cm in temperature
2When being 25(with liquid hourly space velocity with respect to the liquid alkane mixing raw material
-1, i.e. liquid alkane volume/catalyst volume per hour) under carry out.
Each test was carried out 30 hours, below what list in the table 2 is the average conversion and the olefine selective of the linear paraffinic hydrocarbons represented with percentage ratio, be to calculate according to the linear paraffinic hydrocarbons that has transformed; Each catalyzer that makes according to embodiment 1～9 described method includes in table.
Table 2
Transformation efficiency selectivity under the catalyzer
Embodiment % %
1 13.7 92.0
2 12.8 92.8
3 13.2 93.0
4 12.7 93.2
5 13.3 94.9
6 13.0 91.8
7 13.6 92.3
8 10.3 95.1
9 12.6 96.0
Embodiment 11
What present embodiment will carry out is long-acting test, the variation tendency of passing in time with shown activity of check embodiment 1,8 and 9 catalyzer and selectivity.
For reaching this purpose, the above-mentioned various catalyzer of 8ml are packed in the microreactor of embodiment 10, and carry out pre-reduction and sulfidizing by the method for describing among the embodiment 10.
Immediately can carry out dehydrogenation reaction test, at 200 hours duration of test that carried out, temperature of reaction is increased to final 470 ℃ gradually from initial 460 ℃, and other test conditions is with the same among the embodiment 10.
In the accompanying drawings: Fig. 1 is the time dependent curve of each activity of such catalysts; Fig. 2 is that the selectivity of catalyst identical with Fig. 1 passed and the curve that changes in time.
Say that more properly abscissa is the time among Fig. 1, hour being unit, ordinate be just-percentage conversion of alkane.
In Fig. 2, abscissa is the time, hour being unit, ordinate be just-the productive rate percentage ratio of alkene.
More properly say activity of such catalysts and the selectivity of the activity of such catalysts of symbol in each figure " △-△ " expression embodiment 1 and selectivity symbol "-" expression embodiment 8; Activity of such catalysts and selectivity among symbol " zero-zero " the expression embodiment 9.
Further result of study to catalyzer practical application of the present invention shows that the basic metal with in the alkaline-earth metal replacement catalyst mixture can improve the catalytic activity under its low temperature, and this displaced another gain is the work-ing life that can prolong catalyzer effectively.
Therefore, the dehydrogenation catalyst for preparing according to special aspects of the present invention is to comprise a kind of solid-state, particulate porous property carrier just as previously noted, deposits on this matrix:
0.1 platinum～1%(weight); 0.1 tin～1%(weight); 0.05 indium～1%(weight); 0.01 thallium～1%(weight) and 0.05～3.5%(weight) a kind of alkaline-earth metal.Above-mentioned percentage ratio is the percentage ratio to total catalyst weight, and indium is between 0.3: 1 to 6: 1 to the weight ratio of thallium, and platinum is between 0.3: 1 to 1.5: 1 to the weight ratio of indium and thallium.
According to this special aspects of the present invention, platinum should remain between 0.5: 1 to 2: 1 the weight ratio of tin, and platinum should remain between 0.1: 1 to 4: 1 the weight ratio of alkaline-earth metal.
The catalyzer of just having described of special aspects preparation according to the present invention, its total amount that contains catalytic metal is 1%～3% of a final catalyst weight, and in described catalytic metal, preferably indium changes between 1: 1 to 5: 1 the weight ratio of thallium, platinum can change between 0.8: 1 to 1: 1 the weight ratio of indium and thallium, platinum can change between 0.8: 1 to 1: 1 the weight ratio of tin, and platinum can change between 0.2: 1 to 2.5: 1 the weight ratio of alkaline-earth metal.
Magnesium is the preferred alkaline-earth metal of institute.
With regard to this special aspects prepares with regard to the catalyzer according to the present invention, used carrier is with aforesaid the same, and this preface part at this specification sheets is described in conjunction with containing alkali-metal catalyzer, has also quoted reference, and General Principle also is the same; Also all can be included in the aforesaid embodiment 1～10 as for Preparation of catalysts and use.
The following examples 12～14 are to be used for illustrating particular embodiment of the present invention, are to replace basic metal with alkaline-earth metal in this scheme.Embodiment 15 and 16 is used for showing the performance of described catalyzer in the dehydrogenation trial run.
Embodiment 12
The carrier that the preparation catalyzer is used is commercially available gama-alumina, has following technical specification:
Specific surface area 196m
2/ g
Total pore volume 0.75mL/g
Particle size 1.25～1.6mm
To the above-mentioned gama-alumina of 90g, under agitation slowly add the aqueous solution that 120mL is made into by 0.09g thallium trinitrate (TTN) (I), 0.95g five nitric hydrate indiums, 0.9g tin chloride, 2.1g Platinic chloride (Pt that contains 16% weight), 1.5g magnesium nitrate hexahydrate and 6g65% nitric acid.
In envrionment temperature (20～25 ℃) with under stirring, continue contact 1 hour, subsequently reactant was heated to 120 ℃ in 1 hour under airflow, so that virtually completely evaporate excessive water.
In retort furnace, under 500 ℃, calcination is 4 hours in airflow, can obtain a kind of catalyzer with the exsiccant solids that obtains thus, and its composition is listed in the table 3.
Embodiment 13
To this commercially available gama-alumina that 90g embodiment 12 described, under agitation slowly add the aqueous solution of 120mL by 2.6g Platinic chloride (Pt that contains 16% weight), 1.0g tin chloride and the preparation of 6g65% nitric acid.After envrionment temperature (20～25 ℃) contacts one hour down, and under continuously stirring, reactant is heated to 120 ℃ in air, and under this temperature, kept 1 hour, so that really evaporate excessive water fully.
At this moment prepare the aqueous solution that 100mL contains 0.12g thallium trinitrate (TTN) (I), 1.17g five nitric hydrate indiums and 6g65% nitric acid.
At ambient temperature, above-mentioned solution is slowly joined in the solids that the drying that continues stirring crosses.Envrionment temperature with constantly stir under continue contact 1 hour, subsequently again in airflow, 120 ℃ of stirrings 1 hour down.
In time preparation 100mL contains the aqueous solution of 9.3g magnesium nitrate hexahydrate, at ambient temperature, this solution is slowly joined in the dried solids that stirring, Continuous Contact is 1 hour under envrionment temperature and lasting the stirring again, and again in airflow, 120 ℃ of following stirrings 1 hour.
In retort furnace, under 500 ℃, calcination is 4 hours in airflow with the solids that obtain thus.
One finishes all these operations promptly cools off, and can obtain a kind of catalyzer, and its composition is listed in the table 3.
Embodiment 14
Adopt and embodiment 12 identical operations steps,, and add the following aqueous solution in certain sequence successively to prepare a kind of catalyzer with the commercially available gama-alumina of describing among the 90g embodiment 12:
A) aqueous solution made by 2.4g Platinic chloride (Pt that contains 16% weight), 0.9g tin chloride and 6g65% nitric acid of 100mL;
B) 100mL is by 0.1g thallium trinitrate (TTN) (I), the aqueous solution that 1.1g five nitric hydrate indiums and 17.6g magnesium nitrate hexahydrate are made.
In retort furnace, under 500 ℃, calcination is 4 hours in airflow with impregnated solids.
Can obtain a kind of catalyzer thus, its composition is listed in the table 3.
Embodiment 15
Use prepared catalyzer, carry out the test of linear paraffinic hydrocarbons dehydrogenation with the preparation linear alpha-olefin according to embodiment 12～14.
For reaching this purpose, the various catalyzer of 8mL are installed in the tubulose fixed-bed micro-reactor, and in hydrogen stream, carry out prereduction and handle, reduction reaction temperature is 400 ℃, pressure is 2Kg/cm
2, the reaction times is 15 hours.
Subsequently, each catalyzer is carried out sulfidizing, curing time is long enough to make the S/Pt atomic ratio to reach and is approximately 2: 1.For obtaining this result, in common dehydrogenation reaction mixture material, replenish with by the 5%(volume) mixed gas formed of hydrogen sulfide and nitrogen.At 460 ℃ of temperature, pressure 2Kg/cm
2Following reaction.
After finishing above-mentioned steps, begin formal dehydrogenation test, in dehydrogenation reactor, add by C
10～C
13The gaseous mixture that linear paraffinic hydrocarbons, hydrogen G﹠W are formed.In the mixture, hydrogen is 5: 1 to the mol ratio of linear paraffinic hydrocarbons, and the water content in the mixture is 2000 heavy ppm(weight PPMs).
In addition, dehydrogenation reaction is at 465 ℃ of temperature, pressure 2Kg/cm
2Down and by calculate with respect to the liquid alkane raw material the time during liquid air speed (LHSV) 25(
-1, that is: per hour the volume of liquid alkane divided by catalyst volume) under carry out.
Each test was carried out 30 hours, below table 4 listed embodiment 12～14 preparations various catalyzer, by with respect to transforming that alkane estimates, with the hundred linear paraffinic hydrocarbons average conversion and the olefine selectives that show of numerical table very much.
Table 4
Transformation efficiency selectivity under the catalyzer
Embodiment % %
12 13.3 93.0
13 13.7 93.2
14 13.4 91.0
Embodiment 16
Test for a long time, with the check activity of such catalysts of embodiment 13 and selectivity in time passing and the trend that changes.
For reaching this purpose, this catalyzer of 8mL is contained in the microreactor of embodiment 15, as the foregoing description, catalyzer is carried out prereduction and sulfidizing.
Carry out 200 hours dehydrogenation test subsequently, the test temperature of reaction is between 451～453, and other all conditions are with example 15.
After reaction in 200 hours, this catalyzer can keep it active and selectivity is constant fully.
Claims (16)
1, a kind ofly be used to make linear paraffinic hydrocarbons to be dehydrogenated to the dehydrogenation catalyst of linear alpha-olefin, this catalyzer comprises a kind of solid-state particulate porous carrier, deposit above the carrier at this: the thallium of the indium, 0.01～1% (weight) of the tin, 0.05～1% (weight) of the platinum of 0.1～1% (weight), 0.1～1% (weight), and a kind of metal of from basic metal or alkaline-earth metal, selecting of 0.05～3.5% (weight), above-mentioned percentage ratio is the percentage ratio to total catalyst weight; Between 0.3: 1 to 6: 1, platinum ties up between 0.3: 1 to 1.5: 1 the weight ratio of indium and thallium indium to the weight ratio of thallium.
2, catalyzer according to claim 1, wherein platinum ties up between 0.5: 1 to 2: 1 the weight ratio of tin, and platinum ties up between 0.2: 1 to 2.5: 1 the weight ratio of basic metal or alkaline-earth metal.
3, catalyzer according to claim 1, the metal that wherein deposits on the described solid porous bead-type substrate has: platinum 0.1～1%(weight), 0.1 tin～1%(weight), 0.05 indium～1%(weight), 0.01 thallium～1%(weight), and 0.1～2%(weight) a kind of basic metal, above-mentioned percentage ratio is the percentage ratio to total catalyst weight, indium is between 0.3: 1 to 6: 1 to the weight ratio of thallium, and platinum is between 0.3: 1 to 1.5: 1 to the weight ratio of indium and thallium.
4, according to claim 1 or 3 described catalyzer, wherein platinum is between 0.5: 1 to 2: 1 to the weight ratio of tin, and platinum is between 0.2: 1 to 2: 1 to the basic metal ratio.
5, according to claim 1 or 3 described catalyzer, wherein the platinum of Cun Zaiing, tin, indium, thallium and alkali-metal total amount are 1～3%(weight) between, indium is between 1: 1 to 5: 1 to the weight ratio of thallium, platinum is between 0.8: 1 to 1: 1 to the weight ratio of indium and thallium, and platinum is between 0.3: 1 and 1.5: 1 to alkali-metal weight ratio.
6, catalyzer according to claim 3, basic metal wherein is lithium.
7, catalyzer according to claim 3, wherein said carrier is a gama-alumina, the specific surface area of this gama-alumina is at 100～400m
2Between/the g, total pore volume is between 0.5～1.2mL/g.
8, the method for the catalyzer in the preparation claim 1 or 3 may further comprise the steps:
But be made into the compound of platinum, tin, indium and the thallium of water-soluble pyrolytic decomposition, through the nitric acid acidifying aqueous solution, flood a kind of solid-state particulate porous carrier;
The aqueous solution made from the nitrate or the oxyhydroxide of a kind of alkali-metal oxyhydroxide or a kind of alkaline-earth metal, step process is crossed above the dipping, through the dry carrier of crossing at random;
With the dry carrier of crossing after twice dip treating at random, under 450～550 ℃ of temperature, calcination is 2～8 hours in airflow;
Under 350～500 ℃ of temperature, the catalyzer that step is obtained contacts with hydrogen stream, reduces;
Under 400～500 ℃, the catalyzer that the step reduction is obtained contacts with hydrogen sulfide arbitrarily, carries out sulfidizing;
9, preparation contains the method for the linear alpha-olefin of 9～20 carbon atoms in the molecule, and this method comprises: will send into step in the fixed-bed reactor that each described catalyzer in the claim 1 to 8 is housed by the gaseous mixture that the linear paraffinic hydrocarbons that contains 9～20 carbon atoms in hydrogen and each molecule is formed; In the gaseous mixture, hydrogen is between 1: 1 to 15: 1 to the mol ratio of alkane, and temperature of reaction is 400～550 ℃, and pressure is 0.5～5Kg/cm
2Between, be 5～100 o'clock by the liquid hourly space velocity of calculating with respect to the liquid alkane raw material
-1; From dehydrogenation product, isolate linear alpha-olefin.
10, catalyzer according to claim 1, the metal that wherein is deposited on the described solid porous bead-type substrate has: platinum 0.1～1%(weight); 0.1 tin～1%(weight); 0.05 indium～1%(weight); 0.01 thallium～1%(weight); 0.05 a kind of alkaline-earth metal～3.5%(weight); Above-mentioned percentage number average is the percentage ratio to the gross weight of the catalyzer of making at last; Indium is between 0.3: 1 to 6: 1 to the weight ratio of thallium, and platinum is 0.3: 1 to 1.5: 1 to the weight ratio of indium and thallium.
11, catalyzer according to claim 10, wherein platinum is between 0.5: 1 to 2: 1 to the weight ratio of tin, platinum is between 0.1: 1 to 4: 1 to the weight ratio of alkaline-earth metal.
12, catalyzer according to claim 10, wherein the total amount of the platinum of Cun Zaiing, tin, indium, thallium and alkaline-earth metal is 1～3%(weight) between, and indium to the weight ratio of thallium between 1: 1 to 5: 1, platinum to the weight ratio of indium and thallium between 0.8: 1 to 1: 1, platinum to the weight ratio of tin between 0.8: 1 to 1: 1, platinum to the weight ratio of alkaline-earth metal between 0.2: 1 to 2.5: 1.
13, catalyzer according to claim 1, wherein alkaline-earth metal is a magnesium.
14, according to the catalyzer of claim 10, wherein said carrier is a gama-alumina, and the specific surface area of this gama-alumina is 100～400m
2/ g, total pore volume are between 0.5～1.2mL/g.
15, prepare the method for claim 10 or 13 described catalyzer, may further comprise the steps:
But with the compound system of platinum, tin, indium, thallium and the magnesium of water-soluble pyrolytic decomposition, through the nitric acid acidifying aqueous solution, flood solid-state particulate porous property carrier;
Drying, and under 450～550 ℃ of temperature, in airflow to impregnated carrier calcination 2～8 hours;
Under 350～500 ℃ of temperature, the catalyzer that step is obtained contacts with hydrogen stream, reduces;
Under 400～500 ℃ of temperature, the catalyzer that reduction obtains above making at random contacts with hydrogen sulfide, carries out sulfidizing.
16, prepare the method that contains the linear alpha-olefin of 9～20 carbon atoms in each molecule, this method comprises: will send into step in the fixed-bed reactor that the catalyzer described in the claim 10 to 14 is housed by the gaseous mixture that the linear paraffinic hydrocarbons that contains 9～20 carbon atoms in hydrogen and each molecule is formed, in the gaseous mixture, hydrogen is between 1: 1 to 15: 1 to the mol ratio of alkane, temperature of reaction is between 400～550 ℃, and reaction pressure is 0.5～5Kg/cm
2Between, be 5～100 o'clock by the liquid hourly space velocity of calculating with respect to the liquid alkane raw material
-1; From products of dehydrogenation reactions, isolate linear alpha-olefin.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21559/87A IT1222426B (en) | 1987-07-31 | 1987-07-31 | Dehydrogenation catalyst |
| IT21559A/87 | 1987-12-22 | ||
| IT23149/87A IT1223578B (en) | 1987-12-22 | 1987-12-22 | Dehydrogenation catalyst |
| IT23149A/87 | 1987-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033756A true CN1033756A (en) | 1989-07-12 |
| CN1020418C CN1020418C (en) | 1993-05-05 |
Family
ID=26327932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88104700A Expired - Fee Related CN1020418C (en) | 1987-07-31 | 1988-07-30 | Dehydrogenation catalyst, process for its preparation and its use in producing linear olefins from linear paraffins |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2594464B2 (en) |
| KR (1) | KR920010010B1 (en) |
| CN (1) | CN1020418C (en) |
| ES (1) | ES2008818A6 (en) |
| IN (1) | IN171590B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088396C (en) * | 1997-11-28 | 2002-07-31 | 中国石油化工集团公司 | Ball-aluminium oxide containing lithium |
| CN102380425A (en) * | 2010-09-06 | 2012-03-21 | 中国石油化工股份有限公司 | Dehydrogenation catalyst reduction method |
| CN102380426A (en) * | 2010-09-06 | 2012-03-21 | 中国石油化工股份有限公司 | Activation method of dehydrogenation catalyst |
| CN102909096A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction |
| CN102910998A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Dehydrogenation method for light alkanes |
| CN102909094A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst at low temperature |
| CN102909012A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst |
| CN102909015A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for reductive activation of dehydrogenation catalyst by using CO-containing gas |
| CN103041808A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst for simultaneously performing water vapor dechloridation and activation of catalyst |
| CN103041807A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst for firstly reducing and further vulcanizing during dechloridation process of water vapor |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH074529B2 (en) * | 1987-12-28 | 1995-01-25 | ユーオーピー インコーポレイテッド | Layered catalyst particles for dehydrogenation reaction |
| CN100434407C (en) * | 2006-01-19 | 2008-11-19 | 中国石油化工股份有限公司 | Method for preparing propylene by dehydrogenating propane |
| JP2017165667A (en) * | 2016-03-15 | 2017-09-21 | Ｊｘｔｇエネルギー株式会社 | Manufacturing method of conjugated diene |
| JP2019137661A (en) * | 2018-02-15 | 2019-08-22 | Ｊｘｔｇエネルギー株式会社 | Method for producing alkene |
-
1988
- 1988-07-11 IN IN487/MAS/88A patent/IN171590B/en unknown
- 1988-07-28 JP JP63187044A patent/JP2594464B2/en not_active Expired - Lifetime
- 1988-07-29 ES ES8802781A patent/ES2008818A6/en not_active Expired
- 1988-07-30 CN CN88104700A patent/CN1020418C/en not_active Expired - Fee Related
- 1988-08-01 KR KR1019880009787A patent/KR920010010B1/en active IP Right Grant
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088396C (en) * | 1997-11-28 | 2002-07-31 | 中国石油化工集团公司 | Ball-aluminium oxide containing lithium |
| CN102380426B (en) * | 2010-09-06 | 2013-06-05 | 中国石油化工股份有限公司 | Activation method of dehydrogenation catalyst |
| CN102380425A (en) * | 2010-09-06 | 2012-03-21 | 中国石油化工股份有限公司 | Dehydrogenation catalyst reduction method |
| CN102380426A (en) * | 2010-09-06 | 2012-03-21 | 中国石油化工股份有限公司 | Activation method of dehydrogenation catalyst |
| CN102380425B (en) * | 2010-09-06 | 2013-07-24 | 中国石油化工股份有限公司 | Dehydrogenation catalyst reduction method |
| CN102910998B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Dehydrogenation method for light alkanes |
| CN102909012A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst |
| CN102909015A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for reductive activation of dehydrogenation catalyst by using CO-containing gas |
| CN102909094A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst at low temperature |
| CN102910998A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Dehydrogenation method for light alkanes |
| CN102909096A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction |
| CN102909096B (en) * | 2011-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction |
| CN102909094B (en) * | 2011-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst at low temperature |
| CN102909012B (en) * | 2011-08-01 | 2015-04-01 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst |
| CN103041808A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst for simultaneously performing water vapor dechloridation and activation of catalyst |
| CN103041807A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst for firstly reducing and further vulcanizing during dechloridation process of water vapor |
| CN103041807B (en) * | 2011-10-17 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst for firstly reducing and further vulcanizing during dechloridation process of water vapor |
| CN103041808B (en) * | 2011-10-17 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst for simultaneously performing water vapor dechloridation and activation of catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| IN171590B (en) | 1992-11-21 |
| CN1020418C (en) | 1993-05-05 |
| KR890001634A (en) | 1989-03-28 |
| JPS6451145A (en) | 1989-02-27 |
| KR920010010B1 (en) | 1992-11-10 |
| JP2594464B2 (en) | 1997-03-26 |
| ES2008818A6 (en) | 1989-08-01 |
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