CN85106117A - The catalysis selective hydrogenation of alkynes and diolefine in the monoolefine - Google Patents
The catalysis selective hydrogenation of alkynes and diolefine in the monoolefine Download PDFInfo
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- CN85106117A CN85106117A CN85106117.6A CN85106117A CN85106117A CN 85106117 A CN85106117 A CN 85106117A CN 85106117 A CN85106117 A CN 85106117A CN 85106117 A CN85106117 A CN 85106117A
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- palladium
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- hydrogenation
- hydrogenation technique
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Abstract
From olefin feedstock, remove the fixed bed liquid-phase catalysis of alkynes and diene impurity and select hydrogenation technique.Adopt single hop heat-insulating trickle-bed reactor, in order to α-Al
2O
3Be the palladium catalyst of carrier, contain 5～35% (weight) β-Al in the carrier
2O
33H
2O.Reactor inlet temperatures is 0～5 ℃, and temperature out is less than 60 ℃, pressure 14～35 kilograms per centimeter
2, hydrogen and impurity mol ratio are 1: 1～25, liquid volume air speed 50～70 hours
-1The catalyzer average pore radius is 200～2000 dusts, 20～200 meters of active palladium specific surfaces
2/ gram.Alkynes and diene content all are lower than 5 percent after the hydrogenation reaction.
Description
Involved in the present invention is the catalysis selective hydrogenation of impurities in the monoolefine raw material.
In petrochemical industry, the olefin feedstock that obtains with steam splitting process contains alkynes and diene impurity, makes it can satisfy the polymerization-grade requirement in order to produce highly purified alkene, selects method of hydrotreating can remove these impurity just adopt usually.
Select acetylene hydrogenation hydrocarbon and diene impurity generally to adopt vapor phase process and liquid phase method, liquid-phase hydrogenatin has the lifting capacity height than gas phase hydrogenation, catalyst levels is few, reactor volume is little, temperature of reaction is low, and green oil generating amount is few, and catalyst life is long, advantages such as conserve energy are widely used industrial in recent years.
Different according to reactor pattern and processing condition, the unsaturated hydrocarbons liquid phase selective hydrogenation has two kinds of methods, a kind of is German Baeyer (Bayer) (Hydrocarbon Processing, 49,3,121(1969)) and Alan Jay Lerner (Leuna) (Chem.Teehn., 25,10, method 604(1973)) adopts shell and tube single hop bed isothermal reactor, uses propylene refrigeration between pipe, temperature of reaction and pressure are all lower, propylene and propadiene residual quantity higher (less than 40/1000000ths) behind the hydrogenation.This system is owing to the reactor more complicated, and catalyzer is difficult for filling, and cryogen consumption is big, so there be limited evidence currently of adopts.
Another kind is IFP (IFP) method (U, S, P4347.392(1982); Fr 2077907; Inform.Chim., 214,144(1981)) and being characterized in adopting the adiabatic two section bed bioreactors of non-shell and tube, each section inlet temperature is different with reaction pressure.General inlet temperature is 10～20 ℃, pressure 11～25 kilograms per centimeter
2; Two sections inlet temperatures are 20～40 ℃, and pressure is 20～28 kilograms per centimeter
2; Liquid air speed 50 hours
-1With this understanding, general reactor transformation efficiency is generally 65～69%(weight), residue alkynes and diolefine are removed to respectively less than below 5/1000000ths at second stage reactor.
Adopt the adiabatic trickle-bed reactor manufacturing cost of two sections more cheap than shell and tube reactor, catalyzer loads easily evenly, and the each point resistance is identical in the bed, so material divides Fabric also relatively evenly.But IFP method, inlet temperature are 10～20 ℃, and material need be used C before advancing reactor
3Or C
4Make refrigeration agent, increased the cryogen consumption, and use two sections beds to increase facility investment.
The objective of the invention is to study a kind of liquid phase selective hydrogenation technological process of from the monoolefine raw material, removing alkynes and diene impurity,, reduce investment, increase economic efficiency and simplify the operation with further saving energy.The present invention uses the adiabatic trickle-bed reactor of single hop, uses water as cryogen, can reduce energy expenditure, and a kind of corresponding raw catalyst is provided simultaneously.Raw catalyst has: (1) high reactivity, can carry out hydrogenation reaction under high loading; (2) highly selective, promptly when alkynes and diolefine carry out hydrogenation reaction, the raw material monoolefine does not take place or has only small part generation hydrogenation reaction; (3) low surface acidity is beneficial to the polyreaction of controlling alkynes and diolefine, reduces the polymkeric substance growing amount; (4) high mechanical strength can be resisted in long-term operation the continuous erosion and the repeated regeneration of big quantity of fluid; (5) long lifetime and long regeneration period and easy renovation process can recover original active after the regeneration.Catalyzer with the present invention's preparation has above-mentioned advantage concurrently, and the selection hydrogenation of alkynes and diolefine was effective especially under a large amount of propylene were existed, and was not only applicable to C
3The cut liquid phase selective hydrogenation, and be applicable to C
4, C
5Deng removing alkynes and diolefine in the cut.The operational condition of this technology has bigger handiness.
Catalyzer Ji provided by the present invention is applicable to the single hop bed hydroprocessing, also is applicable to two section bed hydroprocessing technologies, and the inlet temperature wide ranges between 0～50 ℃, all can obtain satisfied hydrogenation result.
The liquid-phase catalysis selective hydrogenation reaction that removes alkynes and diene impurity in the olefin feedstock involved in the present invention carries out in single hop heat-insulating trickle-bed reactor.Be equipped with α-Al in the reactor
2O
3Palladium catalyst for carrier.α-Al
2O
3Carrier is by α-Al
2O
3H
2O, β-Al
2O
33H
2The mixture that O and amorphous hydroted alumina are formed is made.Contain β-Al in the mixture
2O
33H
2O5～35%(weight).Alkynes that contains in the olefin feedstock and diene impurity are by being brought down below 5/1000000ths respectively behind the catalytic hydrogenation reaction.
The propylene that obtains by different cracking process in petrochemical complex is produced, butylene etc. contain alkynes and diene impurity separately or in the mixed fraction, and alkynes can be acetylene, methylacetylene and butine, and diolefine can be propadiene and 1.3-divinyl.
Liquid-phase hydrogenatin technology involved in the present invention, its monoolefine raw material and hydrogen mix under pressure after drying, preheating or be cooled to temperature requiredly in heat exchanger then, material passes through beds continuously with stable flow velocity.Reactor inlet temperatures is 0～50 ℃, and temperature out is no more than 60 ℃; The catalyzer working pressure is generally 14～35 kilograms per centimeter
2The material that this technology allows to enter reactor can have higher temperature, and used water is made cooling agent, thereby reduces energy consumption, and this is one of characteristics of the present invention.
Temperature out according to different alkynes in the raw material and diene impurity content and inlet temperature and permission may need portion of product is circulated.Recycle stock gives first the mixing with raw material and hydrogen before entering reactor.Recycle ratio (the product internal circulating load is than fresh material) generally is no more than 5: 1, preferably is no more than 3: 1.
The shortening selectivity increases with the mol ratio of hydrogen and impurity and reduces, and the amounts of hydrogen that enters reactor reduces the mol ratio of hydrogen and impurity as far as possible under the prerequisite that enough removes alkynes and diene impurity.The mol ratio of hydrogen and impurity is generally 1: 1～2.5, and majority is 1: 1.2～2.0, be preferably 1: 1.2～and 1.6, also can introduce thinner in the hydrogen, as: methane.
In catalytic hydrogenation reaction, in general high liquid air speed can improve selectivity, does not increase selectivity but increase air speed sometimes, so the selection of suitable liquid air speed needs according to skilled operation skill.When air speed is suitable, the low selectivity height of ratio foreign matter content that foreign matter content is high in the raw material.The liquid air speed of shortening was generally 50～170 o'clock
-1, be preferably in 90～165
-1The liquid air speed that the present invention uses is 3～6 times of general two section bed bioreactors.This also is one of characteristics of the present invention.
The used catalyzer of hydrogenation is with α-Al
2O
3Be the palladium catalyst of carrier, alumina supporter is by α-Al
2O
3H
2O β-Al
2O
33H
2The mixture that O and unbodied aluminium hydroxide are formed is made.Contain β-Al in the mixture
2O
33H
2O is 5～35%(weight).Said mixture is with making with sodium metaaluminate in the nitric acid.Carrier is shaped to strip, sheet or granular with general method, is preferably spherical.The carrier diameter is 1～8 millimeter, and its specific surface is less than 50 meters
2/ gram.Alumina balls were 1100～1140 ℃ of roastings 1～8 hour, then by the palladium content of catalyzer requirement, i.e. 0.1～1%(weight), preparation Palladous chloride or palladium nitrate aqueous solution, adjust pH to 3.3～6.0, with suitable atomizer be sprayed on method for preparing and be preheating on 20～50 ℃ the carrier, then 60～120 ℃ of dryings.As mentioned above, the pH value and the spraying process of the good solution of GPRS in catalyst preparation process, the catalyst surface palladium layer thickness that makes gained is 160 microns to 500 microns.Carry the α-Al of palladium
2O
3350～500 ℃ of roastings, preferably be no more than 500 ℃.General roasting time 4～10 hours.Use hydrogen-containing gas convenient pressure and 25～150 ℃ then, be preferably in 50～100 ℃, made catalyst reduction 3～10 hours, making with the aluminum oxide is the palladium catalyst of carrier.The average pore radius of catalyzer is 200～2000 dusts, is preferably 300～1500 dusts, is good with 300～600 dusts especially.Pore size distribution is to have 80% the hole pore radius scope at 100～3000 dusts at least, is preferably in 100～1000 dust scopes.Average pore radius directly influences catalyst activity and selectivity, can be in above-mentioned scope for making average pore radius, and the carrier maturing temperature preferably is no more than 1400 ℃.
Selecting the specific surface area of hydrogenation catalyst generally is 3～30 meters
2/ gram is up to 50 meters
2/ gram, pore volume are generally 0.2～1.0 milliliter/gram, are preferably 0.3～0.6 milliliter/gram.Catalyst surface acidity is 0.002～0.005 mmole pyridine/gram catalyzer, can adopt the pyridine adsorption method normal pressure and 120 ℃ of following mensuration.Catalyst activity palladium specific surface is 20～200 meters
2/ gram is preferably in 40～120 meters
2/ gram, available hydrogen-oxygen titration measuring.Palladium exists with crystallized form, and mean grain size is not less than 25 dusts, generally is not more than 110 dusts.
Catalyzer provided by the invention is applicable to the alkynes in the monoolefine and the catalysis selective hydrogenation of diolefine, and Ji can be used for the single hop bed can be used for two section beds again, also can be used for the fixed bed of other type.
Catalyzer provided by the present invention is specially adapted to the selection hydrogenation of diolefine and alkynes in the propylene feedstocks, can under high liquid air speed and higher inlet temperature, select hydrogenation, the polymkeric substance growing amount is few, has reduced the possibility that catalyzer becomes sticky, and has prolonged operating time and life of catalyst.Catalyst selectivity is good, and can make methylacetylene and propadiene impurity conversion is propylene, and the rare hydrogenation reaction of propylene.Use catalyzer provided by the present invention, can produce chemical grade propylene or polymerization-grade propylene, can make in the propylene cut methylacetylene and propadiene foreign matter content less than thousandth or less than 10 by heat-insulating single hop trickle bed liquid phase selective hydrogenation.
Embodiment 1 aluminium-hydroxide powder contains β-Al of 19%
2O
33H
2O is processed as the ball of 2～4 millimeters of diameters by general forming method, and dry back was 1350 ℃ of following roastings 2.5 hours.
With the pH value be 4.2 palladium chloride aqueous solution by atomizer spray wine at carrier surface, the wet bulb that will contain palladium then is dry down at 80 ℃.
With hydrogen 70～90 ℃ and 13 kilograms per centimeter
2Pressure reduced 4～8 hours down.
β-Al in embodiment 2 aluminium-hydroxide powders
2O
33H
2O accounts for 19%(weight), be processed into the ball of 2～3 millimeters of diameters by general forming method, dry back was 1150 ℃ of roastings 4 hours.
With the pH value be 3.6 palladium chloride aqueous solution spray wine on carrier, the wet bulb that contains palladium is dry down at 80 ℃.
Reduced 4～8 hours under 70～90 ℃ and normal pressure with hydrogen then.
The rerum natura of catalyzer of pressing embodiment 1 and embodiment 2 preparations is as follows:
Embodiment 1 embodiment 2
Bulk density, grams per milliliter 0.93 0.90
Specific surface area, rice
2/ gram 4.0 15
Pore volume, milliliter/gram 0.37 0.40
Average pore radius, dust 1,350 520
Palladium content, weight % 0.39 0.27
Surface acidity, mmole pyridine/gram catalyzer 0.017 0.03
The active palladium surface-area, rice
2/ gram 40 115
The palladium mean grain size, dust 103 30
Embodiment 3 catalyzer are pressed embodiment 1 preparation, adopt single hop heat-insulating trickle bed to carry out propylene and select hydrogenation, and hydroconversion condition is as follows:
Experiment A experiment B
Inlet temperature, ℃ 40 40
Temperature out, ℃ 60 57
Pressure (gauge pressure), kg/cm
225.2 23.5
The liquid air speed, hour
-1165 109
Hydrogen/methylacetylene+propadiene, mol ratio 1.60 1.9
The hydrogenation result is as follows:
Experiment (volume %)
Experiment A experiment B
Charging discharging charging discharging
Propane 3.14 3.54 2.26 3.55
Propylene 94.66 96.46 95.31 96.45
Methylacetylene 1.24＜5ppm 0.79＜5ppm
Propadiene 0.96＜5ppm 0.64＜5ppm
C
4Total amount trace/trace/
Experiment A, experiment B C in the material behind hydrogenation
+ 6Content is respectively 0.025%(weight), 0.04%(weight).
Embodiment 4 catalyzer adopt the adiabatic drip fixed bed of single hop with embodiment 2, carry out propylene and select hydrogenation, and hydroconversion condition is as follows:
Inlet temperature, ℃ 39
Temperature out, ℃ 58
Pressure (gauge pressure), kg/cm
222.5
The liquid air speed, hour
-1109
Hydrogen/methylacetylene+propadiene, mol ratio 1.32
The hydrogenation result is as follows:
Volume %
The charging discharging
Propane 2.96 3.12
Propylene 94.89 96.88
Methylacetylene 1.14＜5ppm
Propadiene 1.01＜5ppm
C in the material behind the hydrogenation
+ 6Content is 0.07%(weight).
The present invention also can reduce cost except having the above advantage, reduce cost, conserve energy.
Claims (11)
1, a kind of fixed bed liquid-phase catalysis that removes alkynes and diene impurity from olefin feedstock is selected hydrogenation technique, it is characterized by: adopt single hop heat-insulating trickle bed hydrogenator, be equipped with α-Al in the reactor
2O
3Palladium catalyst for carrier; Carrier α-Al
2O
3Be by α-Al
2O
3H
2O, β-Al
2O
33H
2The mixture that O and amorphous hydroted alumina are formed is made; β-Al in the mixture
2O
33H
2O accounts for 5～35% (weight); Olefin feedstock is by behind the catalytic hydrogenation reaction, and two kinds of foreign matter contents are lower than 5/1000000ths respectively.
2, hydrogenation technique according to claim 1 is characterized in that: the inlet temperature of reaction mass is 0～50 ℃, and temperature out is less than 60 ℃, and used water is as cooling agent, and reaction pressure is 14～35 kilograms per centimeter
2, the mol ratio of hydrogen and impurity is 1: 1～2.5.
3, hydrogenation technique according to claim 1 is characterized in that: the liquid volume air speed is 50～170 o'clock
-1, be preferably at 90～160 o'clock
-1
4, hydrogenation technique according to claim 1 is characterized in that: the vaporization rate of raw material in hydrogenation process can surpass or be lower than 5%.
5, the used support of the catalyst of hydrogenation technique according to claim 1, it is characterized in that: carrier is by α-Al
2O
3H
2O, β-Al
2O
33H
2The mixture that O and amorphous hydroted alumina are formed was made 1100～1400 ℃ of following roastings in 1～8 hour.
6, the used support of the catalyst of hydrogenation technique according to claim 1 is characterized in that: specific surface area is generally 3～30 meters
2/ gram is up to 50 meters
2/ gram.
7, the used catalyzer of hydrogenation technique according to claim 1 is characterized in that: pore volume is generally 0.2～1.0 milliliter/gram, is preferably 0.3～0.6 milliliter/gram.
8, the used catalyzer of hydrogenation technique according to claim 1, it is characterized in that: the average pore radius of catalyzer is 200～2000 dusts, is preferably 300～1500 dusts, preferably 300～600 dusts; Pore size distribution is to have 80% hole at least in the pore radius scope of 100～3000 dusts, is preferably in 100～1000 dust scopes.
9, the used Preparation of catalysts method of hydrogenation technique according to claim 1 is characterized in that: with the pH value is that 3.3～6.0 Palladous chloride or palladium nitrate aqueous solution are sprayed on the carrier, makes the content of palladium on carrier reach 0.1～1.0%(weight).
10, the used catalyzer of hydrogenation technique according to claim 1 is characterized in that: palladium mainly carries and overlays on α-Al
2O
3The top layer on, the palladium layer thickness is 160～500 microns, the specific surface area of active palladium is 20～200 meters
2/ gram, palladium is a crystal type, its mean grain size is not less than 25 dusts.
11, the used catalyzer of hydrogenation technique according to claim 1 is characterized in that: the surface acidity of catalyzer is 0.002～0.05 mmole pyridine/gram catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106117.6A CN1005268B (en) | 1985-08-16 | 1985-08-16 | Catalytic selective hydrogenation of alkynes and dialkenes in mono-alkenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106117.6A CN1005268B (en) | 1985-08-16 | 1985-08-16 | Catalytic selective hydrogenation of alkynes and dialkenes in mono-alkenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106117A true CN85106117A (en) | 1986-10-29 |
| CN1005268B CN1005268B (en) | 1989-09-27 |
Family
ID=4794894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106117.6A Expired CN1005268B (en) | 1985-08-16 | 1985-08-16 | Catalytic selective hydrogenation of alkynes and dialkenes in mono-alkenes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005268B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049680C (en) * | 1997-09-23 | 2000-02-23 | 中国石油化工集团公司 | Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction |
| CN1084222C (en) * | 1998-06-10 | 2002-05-08 | 中国石化齐鲁石油化工公司 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
| CN100389874C (en) * | 2006-07-14 | 2008-05-28 | 谷育英 | Catalyst and its preparing process and usage method and use |
| CN102911714A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Selective hydrogenation method for C5 fraction of ethylene cracking by-product |
| CN102921471A (en) * | 2011-08-10 | 2013-02-13 | 中国石油化工股份有限公司 | Alumina source composition for synthesizing alpha-alumina carrier, alpha-alumina carrier, preparation method of alpha-alumina carrier, silver catalyst, and application of alpha-alumina carrier and silver catalyst |
| CN101434508B (en) * | 2008-12-11 | 2013-07-31 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
| CN103721712B (en) * | 2012-10-12 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of ethylene produces oxirane silver catalyst |
-
1985
- 1985-08-16 CN CN85106117.6A patent/CN1005268B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049680C (en) * | 1997-09-23 | 2000-02-23 | 中国石油化工集团公司 | Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction |
| CN1084222C (en) * | 1998-06-10 | 2002-05-08 | 中国石化齐鲁石油化工公司 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
| CN100389874C (en) * | 2006-07-14 | 2008-05-28 | 谷育英 | Catalyst and its preparing process and usage method and use |
| CN101434508B (en) * | 2008-12-11 | 2013-07-31 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
| CN102911714A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Selective hydrogenation method for C5 fraction of ethylene cracking by-product |
| CN102921471A (en) * | 2011-08-10 | 2013-02-13 | 中国石油化工股份有限公司 | Alumina source composition for synthesizing alpha-alumina carrier, alpha-alumina carrier, preparation method of alpha-alumina carrier, silver catalyst, and application of alpha-alumina carrier and silver catalyst |
| CN102921471B (en) * | 2011-08-10 | 2015-07-22 | 中国石油化工股份有限公司 | Alumina source composition for synthesizing alpha-alumina carrier, alpha-alumina carrier, preparation method of alpha-alumina carrier, silver catalyst, and application of alpha-alumina carrier and silver catalyst |
| CN103721712B (en) * | 2012-10-12 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of ethylene produces oxirane silver catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005268B (en) | 1989-09-27 |
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