CN1145891A - Catalytic hydrogenation process of industrial C5 fraction to produce pentane - Google Patents
Catalytic hydrogenation process of industrial C5 fraction to produce pentane Download PDFInfo
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- CN1145891A CN1145891A CN 95111774 CN95111774A CN1145891A CN 1145891 A CN1145891 A CN 1145891A CN 95111774 CN95111774 CN 95111774 CN 95111774 A CN95111774 A CN 95111774A CN 1145891 A CN1145891 A CN 1145891A
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Abstract
Industrial C5 fraction, a side product of cracking petroleum, is a mixture of saturated and unsaturated components, in which non-straight chain unsaturated C5 component constitutes the majority. In the present invention, it is used as raw material to produce pentane through catalytic hydrogenation in the presence of hydrogenation catalyst. The said method makes it possible to make rational use of C5 fraction.
Description
The present invention is the method for relevant industrial C 5 fraction through shortening manufacturing pentane, specifically, is the method for making pentane about industrial C 5 fraction through shortening.
Pentane is a kind of industrial chemicals, and it can be used as the basic raw material of solvent, whipping agent and other Chemicals.Pentane normally obtains from the straight run process of petroleum hydrocarbon and hydrocracking process, and is a small amount of then make by the C 5 fraction hydrogenation after purifying.Along with the operation in succession of the development of petrochemical complex, particularly ethylene unit, the resource of industrial C 5 fraction also increases year by year.At present, the development and use of industrial C 5 fraction mainly contain two kinds of forms: the one, industrial C 5 fraction is separated the back utilization, and another is that industrial C 5 fraction is not done to separate and directly be used.
Utilization after industrial C 5 fraction separates mainly is the diolefin component of isolating wherein, is used as industrial chemicals.It takes out the production that surplus part can be used for alkylate oil and tert amyl methyl ether(TAME) (TAME).But, because industrial C 5 fraction is made up of the close compound of multiple boiling point, component complexity not only, isomer is more, but also may generate the azeotrope of binary or ternary component, therefore separates comparatively difficult.
C 5 fraction utilizes without separating directly, is mainly used in the production in petroleum resin, tert amyl methyl ether(TAME) fields such as (TAME).Do not see the reported in literature that utilizes industrial C 5 fraction to make pentane through shortening as raw material.
The purpose of this invention is to provide a kind of industrial C 5 fraction that utilizes, particularly utilize not separated industrial C 5 fraction, make the method for pentane through shortening as raw material.
Pentane manufacture method of the present invention is finished as follows.
Industrial C 5 fraction is mainly derived from straight run, hydrocracking, catalytic cracking process and the steam cracking process of petroleum hydrocarbon.Its main component of the industrial C 5 fraction that produces in straight run and hydrocracking process is the pentane, and the industrial C 5 fraction that produces in other process is the mixture of unsaturated component and saturated component, and wherein major part is the unsaturated carbon five of non-straight chain.
Method of the present invention is exactly directly to utilize industrial C 5 fraction to be raw material, under selected reaction conditions, in the presence of catalyzer, by wherein unsaturated component is carried out catalytic hydrogenation reaction, thereby makes pentane.This industrial C 5 fraction comes from by product in the catalytic cracking process of petroleum hydrocarbon or the cracking ethylene preparation process of petroleum hydrocarbon.Wherein, can be the mixture that is rich in monoolefine, or be rich in the mixture of monoolefine and diolefin.Can be extracting also behind the diolefin takes out surplus mixture.
The temperature of reaction of catalytic hydrogenation reaction is 60～200 ℃, preferably 90～150 ℃ temperature range.When the diolefin content in the reaction raw materials is higher, then improve temperature of reaction to reacting favourable.Reaction pressure is 0.05～5MPa, and pressurize is to reacting favourable, but considers actual net effect, and reaction pressure is advisable with 0.2～1.0MPa.Proportioning raw materials is generally 0.5～10 with the molar ratio computing of hydrogen and industrial C 5 fraction, but with 2～5 for well.When diolefin content was higher in the raw material, the mol ratio that improves hydrogen and C 5 fraction was to reacting favourable.The liquid hourly space velocity of C 5 fraction is desirable 0.3～9hr usually
-1, 0.5～2hr preferably
-1When the diolefin content in the raw material is higher, suitably reduce liquid hourly space velocity to the reaction carry out favourable.
The used catalyzer of catalytic hydrogenation reaction is common hydrogenation type catalyzer, can use noble metal carrier catalyst or base metal type catalyzer.
Noble metal carrier catalyst can be expressed as: A/C.
A: representing metallic element palladium, platinum, ruthenium, rhodium or their mixture, is the preferable alloy element with palladium and platinum wherein.Content is generally 0.01～15%, and preferable content range is 0.03～10%.
C: represent carrier, as aluminum oxide, silicon oxide or its mixture, or activated carbon, wherein aluminum oxide and activated carbon are preferred carriers.
Base metal type catalyzer can be expressed as: BXNi
Y/ C
1
B: representing metallic element copper, cobalt, chromium, iron, molybdenum, aluminium, silver or their mixture, is preferred elements with copper, cobalt wherein.
C
1: representing carrier, as the mixture of diatomite, aluminum oxide, silicon oxide, activated carbon or aluminum oxide and silicon oxide, is preferred vector with diatomite, aluminum oxide wherein.Perhaps C
1Represent blank.
The content of metallic element component accounts for 10～50% of whole catalyst weight, and X gets 0～2 in the formula, and Y desirable 1～12.
Above-mentioned catalyzer can be prepared with common catalyzer manufacture method.As noble metal carrier catalyst Pd/Al
2O
3, available an amount of palladium chloride solution dipping Al
2O
3Bead, use drying, reduction back.Base metal type catalyst n i-Cu/ diatomite can add finely powdered diatomite in corresponding nitrate solution, heated and stirred forms uniform paste-like material then, more after filtration, dry, moulding, uses oxygen reduction before the use.
Industrial C 5 fraction is different according to its source, and the wherein contained monoolefine and the kind of diolefin and content difference are very big, but the chemical property of unsaturated olefin is different.Because carbon pentaene key chemical property is all relatively more active, under the effect of hydrogenation type catalyzer, catalytic hydrogenation takes place easily, thereby makes unsaturated link(age) become saturated bond, chemical equation is as follows.
Hydrogenation reaction is finished in fixed-bed reactor, Gu gas-or gas-liquid-solid phase under, carry out in the mode of successive reaction or rhythmic reaction.Under selected processing condition, the reaction mass industrial C 5 fraction with enter well heater after hydrogen mixes, the reaction mass of heater outlet enters catalytic bed with the form of gas phase or gas-liquid mixture material, and the product behind the hydrogenation obtains the pentane product after common condensation separation.
Adopt pentane manufacture method provided by the present invention, can make industrial C 5 fraction after catalytic hydrogenation, the per pass conversion of carbon pentaene hydrocarbon wherein reaches more than 83%, and the per pass conversion of diolefin can reach more than 86%, and the yield of pentane then can reach more than 89%.Therefore, method provided by the present invention is utilizing industrial C 5 fraction to make in this technical field of pentane through shortening for raw material, beyond doubt an of great value method.
Adopt embodiment to explain method of the present invention below.Embodiment 1:
Industrial C 5 fraction mixes with the hydrogen of respective amount after metering, behind the reaction mass well heater, enters the fixed-bed reactor that have the water of condensation chuck.Reaction product is collected liquid product after condensation separation, and with gas chromatograph analysis, check.
Raw material: hydrogen: common steel cylinder hydrogen, purity is greater than 99.5%; Industrial C 5 fraction: take from the by product in the naphtha cracking process of producing ethylene, wherein
The diolefin major part by extracting, take out that monoolefine contains in the surplus mixture
Amount 90%, alkane 8.5%, residue diolefin content 1.5%;
Catalyzer:
Noble metal carrier catalyst Pd/Al
2O
3, Pd content 0.03%, Φ 4 * 4 columns, reaction loading capacity 100ml uses behind 250 ℃ of hydrogen reducings.
Reaction conditions: temperature: 90 ℃; Pressure: 0.1MPa; Hydrogen/molar equivalent: 2; Liquid hourly space velocity: 1.6hr
-1
Reaction result: olefin conversion: 96%; Pentane yield: 98%; Skellysolve A accounts for the pentane total amount: 70%.Embodiment 2:
Raw material: industrial C 5 fraction: take from the by product in the naphtha cracking process of producing ethylene, be regardless of
From diolefin wherein, its composition be monoolefine content 49.5%,
Diolefin 45%, alkane 5.5%.
Reaction conditions: temperature: 105 ℃; Pressure: 0.3MPa; Hydrogen/molar equivalent: 5; Liquid hourly space velocity: 0.8hr
-1
All the other are all identical with embodiment 1.
Reaction result: monoolefine transformation efficiency: 89%; Diolefin transformation efficiency: 93%; Pentane yield: 91%; Skellysolve A accounts for the pentane total amount: 68%.Embodiment 3:
Catalyzer:
Noble metal carrier catalyst Pt/Al
2O
3, Pt content 0.4%, Φ 3 beads.
Preparation process:
1, with diameter of phi 3, specific surface 200m
2The spherical alumina of/g is heated to 200 ℃, takes by weighing 200g after cold.
2, the 50g that gets wherein immerses in the water, blots outside surface moisture content with filter paper again, weigh 69g.
3, preparation 5% sodium carbonate solution 57g immerses remaining 150g aluminum oxide in the step 1 wherein, is heated to 200 ℃ then, and keeps 2 hours.
4, preparation 1.8% platinum acid chloride solution 57g immerses the aluminum oxide in the step 3 wherein, then 150 ℃ dry down, 300 ℃ of following roastings 2 hours.
5, remove chlorion with the distillation water law, then 150 ℃ of dryings.
6, get 100ml by the catalyzer that makes in the step 5, in 300 ℃ of hydrogen streams, activate.
All the other are all identical with embodiment 1.
Reaction result: olefin conversion: 95%; Pentane yield: 93%; Skellysolve A accounts for the pentane total amount: 67%.Embodiment 4:
Catalyzer: base metal type catalyst n i-Cu/ diatomite, the atomic ratio of nickel and copper is 9, and the total amount of nickel and copper accounts for 40% of whole catalyzer, and granularity is the small-particle between 5～10 orders.
Its preparation process is as follows:
Prepare the nitrate solution 21 of nickeliferous 183g and copper 21g, with 500g diatomite input wherein, be heated with stirring to 70 ℃.Slowly feed 10% sodium bicarbonate then, reach 8 until the pH value of paste-like liquid.Continue then to stir 5 hours, filter again.Filter cake is dry under 150 ℃, pulverizes the back 500 ℃ of following roastings 6 hours.Compressing tablet, pulverizing are shaped to the small-particle between 5～10 orders then.Under 400 ℃, use hydrogen reducing before using.
Reaction conditions: temperature: 130 ℃; Pressure: 0.6MPa; Hydrogen/molar equivalent: 7; Liquid hourly space velocity: 0.3hr
-1
All the other are all identical with embodiment 1.
Reaction result: monoolefine transformation efficiency: 87%; Pentane yield: 90%.
Claims (3)
1, a kind of manufacture method of pentane, it is characterized in that with the industrial C 5 fraction being raw material, in the presence of the hydrogenation type catalyzer, temperature of reaction be 60～200 ℃, reaction pressure be 0.05～5MPa, hydrogen/molar equivalent be 0.5～10 and the liquid hourly space velocity of C 5 fraction be 0.3～9hr
-1Condition under, make alkene in the industrial C 5 fraction and hydrogen produce catalytic hydrogenation reaction, thereby make pentane.
2, according to the described pentane manufacture method of claim 1, the industrial C 5 fraction that it is characterized in that being utilized wherein can be the mixture that is rich in monoolefine, the mixture that is rich in monoolefine and diolefin from the catalytic cracking process of petroleum hydrocarbon or the by product in the cracking ethylene preparation process of petroleum hydrocarbon.Can be extracting also behind the diolefin takes out surplus mixture.
3,, it is characterized in that used hydrogenation type catalyzer is: the base metal type catalyzer that contains palladium, platinum, ruthenium, rhodium or copper, cobalt, chromium, iron, molybdenum, aluminium, silver or their mixture according to the described pentane manufacture method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111774A CN1055282C (en) | 1995-09-21 | 1995-09-21 | Catalytic hydrogenation process of industrial C5 fraction to produce pentane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111774A CN1055282C (en) | 1995-09-21 | 1995-09-21 | Catalytic hydrogenation process of industrial C5 fraction to produce pentane |
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| Publication Number | Publication Date |
|---|---|
| CN1145891A true CN1145891A (en) | 1997-03-26 |
| CN1055282C CN1055282C (en) | 2000-08-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111774A Expired - Fee Related CN1055282C (en) | 1995-09-21 | 1995-09-21 | Catalytic hydrogenation process of industrial C5 fraction to produce pentane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074400C (en) * | 1998-12-10 | 2001-11-07 | 中国石化辽阳石油化纤公司 | Preparation of C5 alkane |
| CN100348560C (en) * | 2004-05-20 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
| CN100572345C (en) * | 2006-12-18 | 2009-12-23 | 中国石油天然气股份有限公司 | Method for preparing isopentane solvent for polyolefin by adopting separation process |
| CN102936183A (en) * | 2012-11-15 | 2013-02-20 | 中国海洋石油总公司 | Method for preparing ethylene splitting material by splitting C4/C5 fraction low temperature hydrogenation |
| CN103304382A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Combined process for comprehensively utilizing partial hydrogenation C5 fraction |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2727053C2 (en) * | 1977-06-15 | 1982-11-25 | Süd-Chemie AG, 8000 München | Adsorptive silicate agent for binding alkaline earth ions |
| JPH0699331B2 (en) * | 1989-11-11 | 1994-12-07 | 日本ゼオン株式会社 | Saturated hydrocarbon manufacturing method |
| DK0519573T3 (en) * | 1991-06-21 | 1995-07-03 | Shell Int Research | Hydrogenation catalyst and process |
-
1995
- 1995-09-21 CN CN95111774A patent/CN1055282C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074400C (en) * | 1998-12-10 | 2001-11-07 | 中国石化辽阳石油化纤公司 | Preparation of C5 alkane |
| CN100348560C (en) * | 2004-05-20 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
| CN100572345C (en) * | 2006-12-18 | 2009-12-23 | 中国石油天然气股份有限公司 | Method for preparing isopentane solvent for polyolefin by adopting separation process |
| CN103304382A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Combined process for comprehensively utilizing partial hydrogenation C5 fraction |
| CN102936183A (en) * | 2012-11-15 | 2013-02-20 | 中国海洋石油总公司 | Method for preparing ethylene splitting material by splitting C4/C5 fraction low temperature hydrogenation |
| CN102936183B (en) * | 2012-11-15 | 2015-04-22 | 中国海洋石油总公司 | Method for preparing ethylene splitting material by splitting C4/C5 fraction low temperature hydrogenation |
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| Publication number | Publication date |
|---|---|
| CN1055282C (en) | 2000-08-09 |
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