CN1017779B - Dehydrogenation catalyst and process for preparing it - Google Patents
Dehydrogenation catalyst and process for preparing itInfo
- Publication number
- CN1017779B CN1017779B CN88104701A CN88104701A CN1017779B CN 1017779 B CN1017779 B CN 1017779B CN 88104701 A CN88104701 A CN 88104701A CN 88104701 A CN88104701 A CN 88104701A CN 1017779 B CN1017779 B CN 1017779B
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- carrier
- tin
- thallium
- weight ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A dehydrogenation catalyst for prodn. of a linear olefin from a linear paraffin, consists of a solid particular porous support where 0.05-1 wt.% of Pt, 0.1-1 wt.% of Sn, 0.1-1 wt.% of Tl and 0-1 wt.% of an alkali metal are supported and the wt. ratio of Sn/Tl is up to 1/1, the wt. ratio of Pt/(Sn+Tl) is 0.15/1-0.5/1.
Description
The present invention relates to a kind of dehydrogenation catalyst and its preparation method.The present invention also relates to this catalyzer and be converted into purposes in the method for normal olefine at straight-chain paraffin.
The normal olefine of carbon atoms number more (for example being equal to or greater than 9) is widely used for the present technique field in the molecule.For example, the normal olefine that on average contains about 12 carbon atoms in each molecule is used to prepare the alkylbenzene with a straight alkyl chain, and this alkylbenzene is again useful intermediates of producing biodegradable detergent.
In the art, use linear alkanes dehydrogenation to produce the existing Several Methods of normal olefine, in these known methods, hydrogen contacts with dehydrogenation catalyst with the air-flow that straight-chain paraffin constitutes, and this reaction is carried out at high temperature and under normal atmosphere or condition of super atmospheric pressure.
The catalyzer that is suitable for this purposes generally contains platinum or a kind of platinum metals, is deposited on silicon-dioxide, and aluminum oxide is on the carrier such as natural or synthetical silico-aluminate.
Can bring into play at these catalyzer under the condition of its dehydrogenation, various side reactions can take place, for example the pyrolysis of alkane and/or alkene, isomerization or cyclisation.And, tending to take place further dehydrogenation reaction, the result makes product have the degree of unsaturation bigger than monoolefine, for example produces diolefine.Best, a kind of in dehydriding common phenomena be the quick passivation of catalyzer, usually with carbon laydown, this down phenomenon limits life of catalyst and constitute heavy burden in the commercial production.
In order to improve activity of such catalysts and selectivity in the dehydriding, during the catalyzer in past was formed, used with one or more other metals platinum or a kind of platinum metals.
For example, the U.S. 3,745, No. 112 patent disclosures be deposited on and contain platinum, tin or a kind of alkali-metal dehydrogenation catalyst on the carrier.The U.S. 3,892, No. 657 patent disclosures be deposited on the platinum that contains on the carrier, the dehydrogenation catalyst of indium and a kind of basic metal or alkaline-earth metal.Disclose a kind of catalyzer in 1,499, No. 297 patents of Britain, it contains platinum, a kind of basic metal and at least a from gallium, and the element of selecting in indium and the thallium, and be carrier with the aluminum oxide.The U.S. 4,486, No. 547 patent disclosures a kind of dehydrogenation catalyst, it contains a kind of platinum metals on carrier, tin, indium and a kind of basic metal or a kind of alkaline-earth metal.
But these catalyzer well known in the prior art are still not completely as good as one wishes in every respect, as the activity in the linear alkanes dehydrogenation process, to the selectivity of useful reaction product and the aspects such as time of above-mentioned activity and selectivity maintenance.
The applicant finds, works as platinum, and tin and thallium match with critical mutual ratio, and resulting catalyzer is formed and can be generated the good and persistent activity of performance in the process of normal olefine at linear alkanes dehydrogenation.
First aspect of the present invention relates to a kind of dehydrogenation catalyst, and this catalyzer is by a kind of solid, and is granular, and the porous carrier constitutes, and deposits weight above and accounts for 0.05% to 1% platinum; Weight accounts for 0.1% to 1% tin; Weight accounts for a kind of basic metal of 0% to 1%; Above-mentioned per-cent all is that tin/thallium weight ratio is equal to or less than 1/1 with respect to the gross weight of catalyzer; Platinum/(tin+thallium) weight ratio is between 0.15/1 to 0.5/1.
In preferred embodiment, the contained catalytic metal gross weight of catalyzer of the present invention is 1.0% to 2.5% of a catalyzer gross weight, and in above-mentioned catalytic metal, tin/thallium weight ratio is between 0.4/1 to 0.8/1.
In some cases, find that alkali-metal existence is favourable in catalyzer of the present invention.Therefore, according to a kind of embodiment of the present invention, catalyzer of the present invention outside tin and the thallium, also contains a kind of basic metal except platinum.In this case, platinum/basic metal weight ratio is comparatively favourable between 0.2/1 to 2.0/1.To select the less weight ratio for use to the less basic metal of nucleidic mass simultaneously.In basic metal, recommend to use lithium.
The appropriate carrier of catalyzer of the present invention is a kind of solid particulate carrier, has large surface area (generally greater than 100 meters
2/ gram), have greater porosity (generally greater than 0.5 milliliter/gram), and, select among aluminum oxide and natural or the synthetic silicoaluminate (Silico-aluminates) generally from silicon-dioxide.
The carrier of recommending is an aluminum oxide, and it is in the γ crystal habit, and surface-area is at 100 to 400 meters
2Between/the gram, the cumulative volume in hole is particulate state between 0.5 to 1.2 milliliter/gram, is suitable for fixed-bed reactor and uses.
This Preparation of catalysts method is as follows:
(1) with water-soluble, at high temperature decomposable platinum, the compound of tin and thallium (being salt specifically) adds acid (being nitric acid specifically) the acidifying aqueous solution and soaks into carrier;
(2) make carrier drying;
When (3) needing, soak into the exsiccant carrier with alkali-metal oxyhydroxide;
(4) make the carrier drying of soaking into through secondary;
(5) at high temperature calcine the exsiccant carrier; And
(6) make through the incinerating catalyst reduction.
For example, soaking in the step for the first time, the compound of use can be a Platinic chloride, tin chloride and thallous nitrate (thallium(1)-nitrate).
Soak into operation and be preferably in room temperature or, carry this solution, ceaselessly stir simultaneously to carrier near under the room temperature.Can soak into once, also can soak continuously for several times till catalytic metal is an amount of.
Drying step (2) generally is just need carry out during greater than the cumulative volume of carrier hole when the volume of dipping solution, and its basic purpose is to remove too much (promptly unabsorbed) solvent.
Such drying is preferably in 100-130 ℃ the temperature range, carries out with air-flow.If use platinum, the solution of the compound of tin and thallium repeatedly floods, and can carry out repeatedly dry.
In available step (3), the dipping operation is carried out according to aforementioned manner, uses the aqueous solution of alkali metal hydroxide to carry out, and the dipping back is drying step (4) then, is still undertaken by aforementioned manner.
In calcining step (5), at 450 to 550 ℃ temperature range internal heating catalyzer, operation is carried out under air-flow.
In reduction step (6), through the incinerating catalyzer, operation is at 350 to 500 ℃ high temperature and at normal atmosphere or be higher than under the atmospheric condition and carry out with hydrogen contact reduction.
According to a kind of embodiment of the present invention, calcining step (5) is carrying out before with alkali metal hydroxide impregnation steps (3).In this case, also can obtain to be suitable for the catalyzer of the object of the invention.
According to another kind of embodiment, carrier is to flood with the compound that contains whole catalytic metals, that is to say, alkali metal compound is added to platinum, in the compound of tin and thallium.At this moment, obviously step (3) and (4) have been omitted.
Handle through the reductive catalyzer with a kind of vulcanizing agent and perhaps is suitable, for example uses hydrogen sulfide, its usage quantity should make sulphur in catalyzer/pt atom ratio equal or greatly most 2/1.This processing is preferably under the typical dehydrogenation condition (400 to 500 ℃) to be carried out, to carrying the hydrogen sulfide air-flow of using nitrogen dilution through reductive catalyzer and reaction mixture.
The catalyzer of Huo Deing shows high activity and selectivity at linear alkanes dehydrogenation in the normal olefine conversion process at last, and these characteristics can be kept and remain unchanged for a long period of time.
Specifically, the straight-chain paraffin that carries out dehydrogenation is the straight-chain paraffin that contains 9 or more carbon atoms (for example 9 to 20, particularly 10 to 14) in the branch.
Catalyzer is placed in the fixed-bed reactor, and to its mixed airflow (molar ratio of hydrogen/alkane is 1/1 to 15/1) of carrying these alkane and hydrogen, dehydrogenation is at 400 to 550 ℃, preferably is higher than normal atmosphere (0.5 to 5 kilograms per centimeter
2) condition under carry out, the hourly space velocity of the liquid alkane stream of conveying is 5 to 100 hours
-1
Alkene is separated from the product of dehydrogenation reaction by original known technology at last.
Following example is that the present invention will be described, is not limiting the scope of the invention.
Example 1
A kind of commodity gama-alumina (gamma-alumina) is used as support of the catalyst, and it has following characteristic:
-surface-area: 196 meters
2/ gram
The cumulative volume in-hole: 0.75 milliliter/gram
-granularity: 1.25-1.6 millimeter
120 milliliters by 0.83 gram thallous nitrate (thallium(I)-ni-trate) and 6 gram 65%(weight ratios) the aqueous solution of nitric acid preparation join lentamente in this gama-alumina of 90 grams, and ceaselessly stir.
This solution and gama-alumina stirred 1 hour down in room temperature (20-25 ℃), blew under 120 ℃ 1 hour with air-flow then, thereby the unnecessary aqueous solution is evaporated especially fully.
Prepare 120 milliliters and contain 0.9 gram tin chloride, 2.2 gram Platinic chlorides (weight of platinum accounts for 16%) and 6 restrain the 65%(weight ratios) the aqueous solution of nitric acid.
This aqueous solution at room temperature is added to above-mentioned exsiccant carrier and does not stop to stir.This solution and carrier at room temperature keep in touch and did not stop in 1 hour to stir, and blow under 120 ℃ temperature one hour with air-flow then.
The exsiccant solid that obtains like this is under air-flow, and under 500 ℃ temperature, calcining is 4 hours in close roaster.
With the catalyzer cooling, the composition of gained catalyzer sees Table 1 at last.
Example 2
This routine method is done according to embodiment 1 substantially, and unique difference is, uses thallium, and the compound dipping of tin and copper is after the exsiccant carrier floods with a kind of aqueous solution again, and this aqueous solution is to add 120 milliliters of water preparations with 1.35 gram lithium hydroxides.
Behind the lithium hydroxide solution dipping, use example 1 described method drying and calcined catalyst again, the composition of gained catalyzer sees Table 1.
Example 3
120 ml water solution of nitric acid preparation with 0.96 gram thallous nitrate (thallium(I)-nitrate), 6 gram 65%(weight ratios).Under room temperature (20-25 ℃), slowly join in the commodity gama-alumina of 90 grams with example 1, do not stop to stir.
After not stopping to stir 1 hour under the room temperature (20-25 ℃), be heated to 120 ℃, under the air-flow effect, kept this temperature 1 hour.
Prepare 120 milliliters and contain 1.2 gram tin chlorides, 3.1 gram Platinic chlorides (platinum weight accounts for 16%) and 6 restrain the 65%(weight ratios) the aqueous solution of nitric acid.
At room temperature, this solution is joined in the above-mentioned drying solid while stirring, at room temperature do not stop to stir 1 hour, under 120 ℃ temperature, keeping 1 hour under the air-flow effect then.
The drying solid that obtains like this, under the air-flow effect, calcining is 4 hours in 500 ℃ close roaster.
At last catalyzer is cooled off, the catalyzer of gained, its composition sees Table 1.
Example 4
1 to 3 controlling catalyst of example is used for the test that linear alkanes dehydrogenation changes into normal olefine.
For this purpose, every kind of catalyzer is put into the tubular microreactor of a fixed bed respectively for each 6 milliliters, make it carry out 5 hours initial reduction reactions under hydrogen stream, reaction conditions is 400 ℃, pressure 2 kilograms per centimeter
2
Then every kind of catalyzer is carried out sulfidizing, approximately reach 2/1 up to the atomic ratio of sulphur/platinum.For this reason, except the conventional mixture of dehydrogenation reaction, also in catalyzer, added a kind of mixture.It contains the 5%(volume ratio) hydrogen sulfide, all the other are nitrogen, the condition of reaction is temperature: 460 ℃, pressure: 2 kilograms per centimeter
2
After above-mentioned processing, carry out the dehydrogenation test, a kind of gaseous mixture of input in reactor, it contains: straight chain (C
10-C
13) alkane, hydrogen G﹠W, the molar ratio of hydrogen/straight-chain paraffin are 5/1, the content of water (weight) is 2 in this mixture, 000ppm.
Ensuing dehydrogenation reaction is carried out under the following conditions: temperature: 488 ℃, and pressure: 2 kilograms per centimeter
2, the hourly space velocity of the liquid alkane mixture of conveying is 25 hours
-1(volume/catalyst volume of liquid alkane/hour).
Every test was carried out 20 hours, when having provided among the use-case 1-3 every kind of catalyzer in following table 2, calculated the conversion percentage of straight-chain paraffin and to the optionally percentage of alkene by the straight-chain paraffin that has transformed.
Table 1
Catalyzer instance number 123
Platinum (% by weight) 0.39 0.39 0.55
Tin (% by weight) 0.45 0.45 0.61
Thallium (% by weight) 0.71 0.71 0.82
Lithium (% is by weight)/0.43/
Table 2
Catalyzer instance number transformation efficiency selectivity
（%） （%）
1 18.5 88
2 18.3 90
3 17.5 90
Claims (7)
1, change into the catalyzer that works in the process of normal olefine at linear alkanes dehydrogenation, by solid, granular and porous carrier forms, and deposits on this carrier: the platinum of 0.05 to 1% (weight ratio): the tin of 0.1 to 1% (weight ratio); 0.1 thallium to 1% (weight ratio); A kind of basic metal of 0 to 1% (weight ratio), above-mentioned percentage ratio all are for the gross weight of catalyzer, and the weight ratio of tin/thallium is equal to or less than 1/1; The weight ratio of platinum/(tin+thallium) is between 0.15/1 to 0.5/1.
2, according to the described catalyzer of claim 1, it is characterized in that: the basic metal that the platinum that exists in catalyzer, tin, thallium maybe may exist, altogether gross weight account for total catalyst weight 1% to 2.5% between, and in above-mentioned catalytic metal, the weight ratio of tin/thallium is between 0.4/1 to 0.8/1.
3, according to the described catalyzer of claim 1, it is characterized in that: platinum/alkali-metal weight ratio is between 0.2/1 to 2.0/1.
4, according to the described catalyzer of claim 3, it is characterized in that: described basic metal is lithium.
5, according to the described catalyzer of claim 1, it is characterized in that: described carrier is a granular r-aluminum oxide (gamma-alumina), and its surface-area is 100 to 400 meters
2Between/the gram, and the cumulative volume in hole is between 0.5 to the 1.2 milliliter/gram.
6,, it is characterized in that this method may further comprise the steps according to the described Preparation of catalysts method of claim 1 to 5:
(1) usefulness is dissolvable in water water, and the nitric acid acidifying aqueous solution that adds of the compound of at high temperature decomposable platinum, tin and thallium soaks into a kind of solid, particulate state and porous carrier;
(2) make carrier drying;
When (3) needing, soak into the exsiccant carrier with alkali-metal oxyhydroxide;
(4) make the carrier drying of soaking into through secondary;
(5) at high temperature calcine the exsiccant carrier, and
(6) make through the incinerating catalyst reduction.
7, in accordance with the method for claim 6, it is characterized in that:
In the described step of at high temperature calcining the exsiccant carrier, the air-flow effect is arranged, temperature between 450 to 500 ℃, about 4 hours of calcination time;
In the described step that makes through the incinerating catalyst reduction, with the hydrogen gas stream reduction, service temperature and will make through reductive catalyzer contact hydrogen sulfide and carry out sulfidizing between 350 to 500 ℃, and service temperature is between 400 to 500 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21558A/87 | 1987-07-31 | ||
| IT8721558A IT1228545B (en) | 1987-07-31 | 1987-07-31 | DEHYDROGENATION CATALYST AND PROCEDURE FOR ITS PREPARATION. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031946A CN1031946A (en) | 1989-03-29 |
| CN1017779B true CN1017779B (en) | 1992-08-12 |
Family
ID=11183583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88104701A Expired CN1017779B (en) | 1987-07-31 | 1988-07-30 | Dehydrogenation catalyst and process for preparing it |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2594463B2 (en) |
| KR (1) | KR920010008B1 (en) |
| CN (1) | CN1017779B (en) |
| ES (1) | ES2008817A6 (en) |
| IN (1) | IN171833B (en) |
| IT (1) | IT1228545B (en) |
Families Citing this family (8)
| 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 |
| ES2151015T3 (en) * | 1994-11-29 | 2000-12-16 | Degussa | CATALYST FOR THE DEHYDROGENATION OF PARAFFINS C6 TO C15. |
| CN1069226C (en) * | 1996-01-24 | 2001-08-08 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN1084224C (en) * | 1997-06-09 | 2002-05-08 | 中国科学院大连化学物理研究所 | Catalyst for dehydrogenation of saturated hydrocarbon and preparation thereof |
| JP4740564B2 (en) * | 2004-08-12 | 2011-08-03 | 千代田化工建設株式会社 | Hydrogen purification method |
| KR101133363B1 (en) * | 2009-12-30 | 2012-04-06 | 주식회사 효성 | Oxidative dehydrogenation aerogel catalyst, and process for preparing propylene from propane using the same |
| 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 |
| KR102175701B1 (en) * | 2018-10-19 | 2020-11-06 | 희성촉매 주식회사 | Method for producing catalysts of high efficiency for dehydrogenation of light branched hydrocarbons |
-
1987
- 1987-07-31 IT IT8721558A patent/IT1228545B/en active
-
1988
- 1988-07-22 IN IN522/MAS/88A patent/IN171833B/en unknown
- 1988-07-26 KR KR1019880009397A patent/KR920010008B1/en active IP Right Grant
- 1988-07-28 JP JP63187043A patent/JP2594463B2/en not_active Expired - Lifetime
- 1988-07-29 ES ES8802780A patent/ES2008817A6/en not_active Expired
- 1988-07-30 CN CN88104701A patent/CN1017779B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IN171833B (en) | 1993-01-23 |
| IT8721558A0 (en) | 1987-07-31 |
| KR890001633A (en) | 1989-03-28 |
| CN1031946A (en) | 1989-03-29 |
| KR920010008B1 (en) | 1992-11-10 |
| JP2594463B2 (en) | 1997-03-26 |
| JPS6451144A (en) | 1989-02-27 |
| ES2008817A6 (en) | 1989-08-01 |
| IT1228545B (en) | 1991-06-20 |
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