CN1256261A - Preparation of C5 alkane - Google Patents
Preparation of C5 alkane Download PDFInfo
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- CN1256261A CN1256261A CN 98121056 CN98121056A CN1256261A CN 1256261 A CN1256261 A CN 1256261A CN 98121056 CN98121056 CN 98121056 CN 98121056 A CN98121056 A CN 98121056A CN 1256261 A CN1256261 A CN 1256261A
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Abstract
The present invention features that industrial C5 fraction is made to effect hydrogenation by using Ziegler catalyst and in selected reaction condition, so that the olefine in the C5 fraction is hydrogenated to become saturated alkane. The conditions for the hydrogenation include reaction temperature of 30-200 deg.c, reaction pressure of 0.1-5.0 MPa and use amount of homogeneous catalyst of 30-3000 ppm. Rectificating the hydrogenated product can obtain serial pentane products. Compared with prior art, the present invention has the advantages of higher catalyst efficiency, mild reaction condition, high olefine conversion and alkane yield, low cost, etc., so that the present invention is one effective way of preparing high quality pentane product.
Description
To be the relevant industrial C 5 fraction prepare the method for C 5 alkane through homogeneous catalytic hydrogenation in the present invention, specifically in the presence of the homogeneous hydrogenation catalyzer, hydrogenation of olefins in the industrial C 5 fraction become the method for saturated carbon 5 alkane.
C 5 alkane comprises Skellysolve A, pentamethylene and iso-pentane, all is exceedingly useful basic chemical raw materials.Particularly in recent years, use pentane (as Skellysolve A or pentamethylene) to replace fluorine Lyons as the application of PU and EPS whipping agent or solvent remarkable progress to be arranged, its market demand increases day by day.By industrial C 5 fraction hydrogenation preparing C 5 alkane, can obtain the required product in market by rectifying again, be an important channel of industrial preparation pentane.
The method of industrial C 5 fraction hydrogenation preparing C 5 alkane, the Chinese patent of existing Shanghai Petrochemical High Training School application, application number are to disclose in 95111774.2 (applying date 95.9.21, open day on March 26th, 1997).This patent of invention is to utilize the non-precious metal type catalyzer that contains palladium, platinum, ruthenium, rhodium or copper, cobalt, chromium, iron, molybdenum, aluminium, silver or their mixture, at 60--200 ℃, 0.05--5.0MPa under the condition, in fixed-bed reactor, finish hydrogenation reaction.The per pass conversion of its carbon pentaene hydrocarbon only is more than 83%, and the yield of pentane also only is more than 89%.As everyone knows, because industrial C 5 fraction is formed very complexity, wherein have and be no lack of the impurity that influences catalyst performance, diolefine also especially easily in the catalyst surface coking, makes catalyzer be difficult to the activity of bringing into normal play, and the hydrogenation effect is subjected to very big influence.Carbon pentaene hydrocarbon per pass conversion and pentane yield are all lower in the above-mentioned patent application, can't but be relevant with its catalyzer that adopts.And, all very complicated, the trouble of this Preparation of catalysts and activation.Also have, the hydrogenation conversion of alkene is low, and it is still very complicated to cause hydrogenation products to form, and can't separate obtaining highly purified pentane product.Simultaneously, the existence of alkene also has bigger influence to the product application performance, must be removed.
Purpose of the present invention is exactly the problem that exists in the above-mentioned prior art in order to solve, heterogeneous catalyst is a homogeneous catalyst in the change technological process, improve the yield of carbon pentaene hydrocarbon conversion rate and pentane, develop a kind of new, high efficiency method for preparing high-quality C 5 alkane.
Technical solution of the present invention is, with the industrial C 5 fraction is raw material, select Ziegler-type homogeneous hydrogenation catalyzer for use, under selected reaction conditions, make the unsaturated hydrocarbons in the C 5 fraction carry out catalytic hydrogenation reaction, produce highly purified C 5 alkane,, can obtain requiring the pentane product of quality again through rectifying separation.
The primary industry C 5 fraction is mainly derived from the by product of petroleum hydrocarbon cracking or catalytic cracking process.Wherein, can be the mixture that is rich in monoolefine, or be rich in the mixture of monoolefine and diolefin that can be extracting also behind the diolefin takes out surplus mixture.Said monoolefine comprises positive amylene, cyclopentenes, isopentene, and diolefin comprises pentadiene, cyclopentadiene, isoprene.
The present invention is owing to adopt the homogeneous hydrogenation catalyzer, active higher, reaction can be carried out under lesser temps and pressure, its temperature of reaction is generally 30 ℃～200 ℃, be preferably 50 ℃～100 ℃, reaction pressure is 0.1～5.0MPa, is preferably 0.5～1.0MPa, the mol ratio of hydrogen and C 5 fraction is generally 1～5, is preferably 1～3.
The homogeneous hydrogenation catalyzer that the present invention adopts is a kind of Ziegler-type catalyst, is reacted through complexing with alkylaluminium cpd by the organic acid salt of transition metal to form.This complex catalyst system is a kind of liquid state, and available volume pump is injected in the reactor easily, and can be dispersed in the reaction system, the efficient of catalyzer is very high, and usage quantity is very low, both can satisfy the hydrogenation needs, its add-on is generally 30～3000ppm, is preferably 100～500ppm.
Because hydrogenation conversion is very high, product contains alkene hardly, and it is big that the each component boiling-point difference becomes, so this product is carried out rectifying, just can obtain high-quality pentane product, Skellysolve A, pentamethylene, iso-pentane etc.
Homogeneous hydrogenation reaction can be carried out in still formula, tower or tubular reactor, is mass transfer and the heat-transfer effect that guarantees reaction, needs in the reaction process to be equipped with and stirs or adopt external circulation mode.Reaction formation both can adopt rhythmic reaction, also can adopt continuous reaction.No matter adopt which kind of reactive mode, all can obtain purity greater than 99% C 5 alkane product.
Outstanding feature of the present invention is with the heterogeneous catalyst technology in the prior art, changes the homogeneous hydrogenation catalyzer into, and it can be dispersed in the reaction system, each active centre of catalyzer all can play a role, therefore, the entire reaction condition relaxes, and the efficient of catalyzer is high especially, carbon pentaene hydrocarbon conversion rate and alkane yield height, corresponding preparation cost is low, for making full use of the industrial C 5 fraction resource, prepares high-quality, the pentane series product of the market requirement provide an effective way.The present invention adopts the homogeneous hydrogenation catalyzer in addition, uses the heterogeneous catalyst defective of coking in reaction process easily thereby overcome prior art.
Below by example, the invention will be further described.
Example 1.
Hydrogen--common steel cylinder hydrogen, purity is greater than 99%.The Ziegler-type catalyst that catalyzer is formed by transition metal organic acid salt and triethyl aluminum complexing.Getting the isocaprylic acid nickel solution that contains isocaprylic acid nickel 2.0g and add in the goat's horn bottle, is that 5.0 ratio is injected triethyl aluminium solution with the Al/Ni mol ratio, gets final product after the reaction.
Industrial C 5 fraction--take from the by product in the naphtha cracking process of producing ethylene, be rich in monoolefine.Wherein monoolefine 85%, diolefin 8%, alkane 7%.
Reaction process: in industrial C 5 fraction and the disposable adding reactor of homogeneous catalyst for preparing above.80 ℃ of temperature, reaction pressure 1MPa, catalyst concn are under the reaction conditions of 300ppm, carry out hydrogenation reaction.When hydrogen-absorption speed is zero, be reaction end.Product carries out rectification process after condensation separation.Isolate Skellysolve A, pentamethylene, iso-pentane successively.Product is analyzed through gas chromatograph.
Reaction result: alkene per pass conversion: 99.24%, 48 minutes hydrogenation reaction time, pentane yield 99.76%.
Example 2.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is taken from the by product in the naphtha cracking process of producing ethylene, is rich in monoolefine.Wherein monoolefine 80%, diolefin 4%, alkane 16%.
Reaction process: removing temperature is 100 ℃, and reaction pressure 1.2MPa, catalyst concn are outside the reaction conditions of 200ppm, and all the other are with example 1
Reaction result: alkene per pass conversion: 99.80%, 54 minutes hydrogenation reaction time, pentane yield 99.53%.
Example 3.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is taken from the by product in the naphtha cracking process of producing ethylene, is rich in diolefin.Wherein diolefin 87%, monoolefine 6%, alkane 7%.
Reaction process: removing temperature is 70 ℃, and reaction pressure 1.6MPa, catalyst concn are outside the reaction conditions of 400ppm, and all the other are with example 1
Reaction result: alkene per pass conversion: 99.54%, 42 minutes hydrogenation reaction time, pentane yield 99.48%.
Example 4.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is taken from the by product in the naphtha cracking process of producing ethylene, is rich in diolefin.Wherein diolefin 90%, monoolefine 4%, alkane 6%.
Reaction process: removing temperature is 90 ℃, and reaction pressure 1.0MPa, catalyst concn are outside the reaction conditions of 200ppm, and all the other are with example 1
Reaction result: alkene per pass conversion: 99.62%, 56 minutes hydrogenation reaction time, pentane yield 99.50%.
Example 5.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is taken from the by product in the naphtha cracking process of producing ethylene, and wherein diolefin 38%, monoolefine 52%, alkane 10%.
Reaction process: removing temperature is 40 ℃, and reaction pressure 0.7MPa, catalyst concn are outside the reaction conditions of 500ppm, and all the other are with example 1
Reaction result: alkene per pass conversion: 99.48%, 40 minutes hydrogenation reaction time, pentane yield 99.74%.
Example 6.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is identical with example 5.
Reaction process: removing temperature is 120 ℃, and reaction pressure 1.0MPa, catalyst concn are outside the reaction conditions of 500ppm, and all the other are with example 1
Reaction result: alkene per pass conversion: 99.62%, 38 minutes hydrogenation reaction time, pentane yield 99.89%.
Example 7.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is taken from the by product in the naphtha cracking process of producing ethylene, with diolefin extracting wherein, takes out monoolefine 92% in the excess, diolefin 2%, alkane 6%.
Reaction process: removing temperature is 70 ℃, and reaction pressure 0.8MPa, catalyst concn are outside the reaction conditions of 300ppm, and all the other are with example 1
Reaction result: alkene per pass conversion: 99.34%, 50 minutes hydrogenation reaction time, pentane yield 99.52%.
Example 8.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is identical with example 7.
Reaction process: removing temperature is 90 ℃, and reaction pressure 1.4MPa, catalyst concn are outside the reaction conditions of 200ppm, and all the other are with example 1.
Reaction result: alkene per pass conversion: 99.24%, 50 minutes hydrogenation reaction time, pentane yield 99.82%.
Example 9.
Raw material: hydrogen, catalyzer are identical with example 1.It is identical with example 2 that industrial C 5 fraction is got.
Reaction process: industrial carbon five and the liquid-gas ratio of hydrogen by 1: 3, enter reactor and carry out successive reaction, 80 ℃ of temperature, reaction pressure 1.0MPa, catalyst concn carries out hydrogenation reaction for the 200ppm reaction conditions.Hydrogenation products carries out gas-liquid separation, and hydrogen recycle is used, and alkane enters rectifying tower and carries out rectification process, isolates Skellysolve A, pentamethylene, iso-pentane successively.After successive reaction is carried out 24 hours, form with the gas chromatograph assay products.
Reaction result: alkene per pass conversion: 99.84%, pentane yield 99.74%.
Example 10.
Raw material: hydrogen, catalyzer, industrial C 5 fraction are identical with example 1.Reaction process: removing temperature is 40 ℃, and reaction pressure 0.3MPa, catalyst concn are outside the reaction conditions of 1500ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 20 hours with example 9.
Reaction result: alkene per pass conversion: 99.10%, pentane yield 99.84%.
Example 11.
Raw material: hydrogen, catalyzer, industrial C 5 fraction are identical with example 1.Reaction process: removing temperature is 150 ℃, and reaction pressure 1.2MPa, catalyst concn are outside the reaction conditions of 400ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 25 hours with example 9.
Reaction result: alkene per pass conversion: 99.79%, pentane yield 99.71%.
Example 12.
Raw material: hydrogen, catalyzer, industrial C 5 fraction are identical with example 1.Reaction process: removing temperature is 80 ℃, and reaction pressure 2.5MPa, catalyst concn are outside the reaction conditions of 250ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 40 hours with example 9.
Reaction result: alkene per pass conversion: 99.40%, pentane yield 99.40%.
Example 13.
Raw material: hydrogen, catalyzer, industrial C 5 fraction are identical with example 1.Reaction process: removing temperature is 30 ℃, and reaction pressure 4.0MPa, catalyst concn are outside the reaction conditions of 300ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 35 hours with example 9.
Reaction result: alkene per pass conversion: 99.31%, pentane yield 99.89%.
Example 14.
Raw material: hydrogen, catalyzer, industrial C 5 fraction are identical with example 1.Reaction process: removing temperature is 90 ℃, and reaction pressure 1.0MPa, catalyst concn are outside the reaction conditions of 500ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 35 hours with example 9.
Reaction result: alkene per pass conversion: 99.84%, pentane yield 99.70%.
Example 15.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is identical with example 3.
Reaction process: removing temperature is 55 ℃, and reaction pressure 0.8MPa, catalyst concn are outside the reaction conditions of 1200ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 30 hours with example 9.
Reaction result: alkene per pass conversion: 99.62%, pentane yield 99.91%.
Example 16.
Raw material: hydrogen, catalyzer, example 1 are identical.Industrial C 5 fraction is identical with example 3.
Reaction process: removing temperature is 80 ℃, and reaction pressure 1.6MPa, catalyst concn are outside the reaction conditions of 200ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 25 hours with example 9.
Reaction result: alkene per pass conversion: 99.50%, pentane yield 99.97%.
Example 17.
Raw material: hydrogen, catalyzer, identical with example 1.Industrial C 5 fraction is identical with example 5.
Reaction process: removing temperature is 105 ℃, and reaction pressure 1.0MPa, catalyst concn are outside the reaction conditions of 500ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 30 hours with example 9.
Reaction result: alkene per pass conversion: 99.80%, pentane yield 100%.
Example 18.
Raw material: hydrogen, catalyzer, identical with example 1.Industrial C 5 fraction is identical with example 5.
Reaction process: removing temperature is 30 ℃, and reaction pressure 3.5MPa, catalyst concn are outside the reaction conditions of 300ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 30 hours with example 9.
Reaction result: alkene per pass conversion: 99.26%, pentane yield 99.96%.
Example 19.
Raw material: hydrogen, catalyzer, identical with example 1.Industrial C 5 fraction is identical with example 7.
Reaction process: removing temperature is 80 ℃, and reaction pressure 1.2MPa, catalyst concn are outside the reaction conditions of 100ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 30 hours with example 9.
Reaction result: alkene per pass conversion: 99.32%, pentane yield 99.78%.
Example 20.
Raw material: hydrogen, catalyzer, identical with example 1.Industrial C 5 fraction is identical with example 7.
Reaction process: removing temperature is 150 ℃, and reaction pressure 2.0MPa, catalyst concn are outside the reaction conditions of 350ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 25 hours with example 9.
Reaction result: alkene per pass conversion: 99.45%, pentane yield 99.99%.
Example 21.
Raw material: hydrogen, catalyzer are identical with example 1.Industrial C 5 fraction is identical with example 7.
Reaction process: removing temperature is 180 ℃, and reaction pressure 3.0MPa, catalyst concn are outside the reaction conditions of 200ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 20 hours with example 9.
Reaction result: alkene per pass conversion: 99.68%, pentane yield 99.94%.
Example 22.
Raw material: hydrogen, catalyzer, identical with example 1.Industrial C 5 fraction is identical with example 7.
Reaction process: removing temperature is 40 ℃, and reaction pressure 0.8MPa, catalyst concn are outside the reaction conditions of 800ppm, and all the other, are formed with the gas chromatograph assay products after successive reaction is carried out 40 hours with example 9.
Reaction result: alkene per pass conversion: 99.48%, pentane yield 99.87%.
Comparative example 1
Catalyzer: non-precious 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 10% of whole catalyzer, and granularity is the small-particle between the 5--11 order.
Its preparation process is as follows:
Prepare 2 liters of the salpeter solutions of nickeliferous 183g and copper 21g, with 500g diatomite input wherein, be heated with stirring to 70 ℃.Then, slowly feed 10% sodium bicarbonate, reach 8 until the pH value of paste-like liquid.Then, continue to stir 5 hours, filter again.Filter cake is dry under 150 ℃, pulverizes the back 500 ℃ of following roastings 65 hours.Compressing tablet is pulverized the small-particle that is shaped between the 5-10 order then, uses hydrogen reducing before using under 400 ℃.
Raw material: hydrogen--common steel cylinder hydrogen, purity is greater than 99%.
Industrial C 5 fraction is taken from the by product in the naphtha cracking process of producing ethylene, and diolefin major part wherein is by extracting, and the monoolefine content of taking out in the surplus mixture is 90%, alkane 8.5%, residue diolefin content 1.5%.
Reaction process: 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, analyze with gas chromatograph.
Reaction conditions: temperature is 130 ℃, and pressure is 0.6MPa, and hydrogen/molar equivalent is 7, and liquid hourly space velocity is 0.3 o'clock
-1
Reaction result: alkene per pass conversion: 87%, pentane yield 90%.
Claims (3)
1. the preparation method of a C 5 alkane, make raw material with industrial C 5 fraction, in the presence of catalyzer, 30～200 ℃ of temperature of reaction, reaction pressure 0.1～5.0MPa, hydrogen/molar equivalent are under 1～5 the condition, make that hydrogenation of olefins is saturated to C 5 alkane in the industrial C 5 fraction, it is characterized in that having adopted Ziegler-type homogeneous hydrogenation catalyzer among the C 5 alkane preparation technology, consumption is generally 30～3000ppm.
2. the preparation method of C 5 alkane according to claim 1 is characterized in that used homogeneous hydrogenation catalyzer is organic acid salt and the alkylaluminium cpd by transition metal, the Ziegler-type catalyst of making through the complexing reaction.
3. the preparation method of C 5 alkane according to claim 1 is characterized in that the homogeneous hydrogenation catalyst consumption is preferably 100～500ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121056A CN1074400C (en) | 1998-12-10 | 1998-12-10 | Preparation of C5 alkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121056A CN1074400C (en) | 1998-12-10 | 1998-12-10 | Preparation of C5 alkane |
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| CN1256261A true CN1256261A (en) | 2000-06-14 |
| CN1074400C CN1074400C (en) | 2001-11-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107573205A (en) * | 2017-10-27 | 2018-01-12 | 濮阳市联众兴业化工有限公司 | One kind is without naphthalene nucleus pentane production method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2161524A5 (en) * | 1971-11-26 | 1973-07-06 | Inst Francais Du Petrole | Ziegler catalyst - reacted in presence of tetrahydro naphtalene for naphthalene hydrogenation |
| US4155832A (en) * | 1977-12-23 | 1979-05-22 | The United States Of America As Represented By The United States Department Of Energy | Hydrogenation process for solid carbonaceous materials |
| CN1055282C (en) * | 1995-09-21 | 2000-08-09 | 上海石油化工高等专科学校 | Catalytic hydrogenation process of industrial C5 fraction to produce pentane |
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1998
- 1998-12-10 CN CN98121056A patent/CN1074400C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107573205A (en) * | 2017-10-27 | 2018-01-12 | 濮阳市联众兴业化工有限公司 | One kind is without naphthalene nucleus pentane production method |
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| CN1074400C (en) | 2001-11-07 |
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