CN1012814B - Homogeneous catalyst of benzene hydrogenization - Google Patents
Homogeneous catalyst of benzene hydrogenizationInfo
- Publication number
- CN1012814B CN1012814B CN88105065A CN88105065A CN1012814B CN 1012814 B CN1012814 B CN 1012814B CN 88105065 A CN88105065 A CN 88105065A CN 88105065 A CN88105065 A CN 88105065A CN 1012814 B CN1012814 B CN 1012814B
- Authority
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- China
- Prior art keywords
- catalyst
- homogeneous catalyst
- benzene
- nickel
- transition metal
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- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a homogeneous catalyst of benzene hydrogenization. In the catalyst, nickel or cobalt as transitional metal is adopted, the metallic nickel is preferably adopted, and negative ions of a compound are carboxylate radicals from C6 to C18. Trialkyl aluminum is used as a cocatalyst, the molecular formula of the trialkyl aluminum is AlR1R2R3, wherein R1, R2 and R3 are respectively alkyl radicals from C1 to C16. Weak organic acids adopted as third catalyst components mainly comprise primary alcohols, secondary alcohols and tertiary alcohols from C1 to C10. The catalyst has the obvious characteristics that water is adopted as a fourth catalyst component, and the synergistic effect of the water and the third components can improve the initial reaction speed of the homogeneous catalyst of benzene hydrogenization to a large extent and prolong the service life of the catalyst.
Description
The present invention relates to a kind of unsaturated hydrocarbons homogeneous hydrogenation Catalysts and its preparation method, be particularly useful for benzene hydrogenation and produce in the reaction of hexanaphthene.
Benzene hydrogenation is produced the homogeneous hydrogenation catalyzer of hexanaphthene, at present for many kinds being arranged known to the public, they are by a kind of transition metal carboxylate salt, and the hydride of its transition metal such as cobalt, titanium, network, iron or nickel etc. and organometallic compound or lithium, sodium, aluminium or their derivative are formed.In order to improve activity of such catalysts and stability, people add a kind of additive or are called the 3rd component in catalyzer, are some strong organic acids.May 23 1980 United States Patent (USP) U.S4357478(applying date, 2 days November nineteen eighty-two of date of publication)＜the unsaturated compound method of hydrotreating〉in, introduced unsaturated compound employed homogeneous catalyst in hydrogenation process, by a kind of transition metal carboxylate salt (the appellation Primary Catalysts or first component), preferred transition metal is the carboxylate salt of cobalt or nickel, as two Cobaltous diacetates, two nickel acetates, nickel naphthenate, nickel stearate, cobalt of ethyl hexanoate, nickel benzoate, capric acid nickel and reductive agent compound trialkyl aluminium are as triethyl aluminum or triisobutyl aluminium (the appellation promotor or second component) and at least one strong carboxylic acid (appellation additive or the 3rd component) composition.Strong carboxylic acid is a kind of organic carboxyl acid (KPa in 25 ℃ of water less than 7), and these acid contain 1～25 carbon atom, are preferably the carboxylic acid of 6～25 carbon atoms.
The mol ratio of reductive agent and transition metal carboxylate salt is 0.5: 1～10: 1 in the homogeneous catalyst, preferably 1.5: 1～6: 1; The mol ratio of strong carboxylic acid and transition metal carboxylate salt is 0.05: 1～1: 1; The temperature of reaction of producing homogeneous catalyst is 0～200 ℃, and the best is 70～160 ℃.
Succeeding in developing and industrial application of above-mentioned homogeneous catalyst removed the unsafe factor that Raney's nickel catalyst brings for the benzene hydrogenation production equipment.The homogeneous catalyst injecting reactor is compared with Raney's nickel catalyst, and is easy and simple to handle, and the maintenance of its recycle system and injected system also reduces significantly, and running period is also long than Raney's nickel catalyst.Although described homogeneous catalyst has obvious improvement than existing solid phase Raney's nickel catalyst, can't say flawless.The 3rd component organic carboxyl acid in the above-mentioned catalyzer has been selected strong carboxylic acid for use, under High Temperature High Pressure hydrogenation unit is corrosive; The existence of water is regarded as the poisonous substance of Ziegler-type catalyst.
The objective of the invention is, on the basis of above-mentioned homogeneous catalyst, selecting weak organic acid for use is the 3rd component, increase water as the 4th component, overcome the corrosive defective of above-mentioned homogeneous catalyst to hydrogenation unit, main is the speed of response that improves homogeneous catalyst, prolongs life of catalyst.
The reactive metal of benzene hydrogenating homogeneous catalyst of the present invention is selected transiting metal nickel or cobalt for use, preferentially select metallic nickel for use, the negatively charged ion of its compound is the carboxylate radical of C6～C8, as caproic acid root, enanthic acid root, sad, isocaprylic acid root, n-nonanoic acid root, decanoate, benzoate anion, stearate radical, oleic acid root and cycloalkanes acid group, with trialkyl aluminium is promotor, appellation second component or reductive agent.Wherein molecular formula is ALR1R2RB3, and wherein R1, R2, R3 are respectively C1～C16 alkyl, for example triisobutyl aluminium, trimethyl aluminium, triethyl aluminum, triphenyl aluminum and hexadecyl aluminium.Selecting weak organic acid for use is catalyzer the 3rd component, be mainly C1～C10 primary, secondary, the tertiary alcohol, as the trimethyl carbinol, tertiary amyl alcohol, hexanol, 2-Ethylhexyl Alcohol, butanols, octanol, hexalin.Water is complementary with it as the 4th component of catalyzer in addition.
The mole number of triethyl aluminum and transition metal carboxylate salt mole ratio are 1: 1～8: 1, are preferably 2: 1～5: 1.The mole number of weak organic acid and transition metal carboxylate salt mole ratio are 0.1: 1～1: 1, preferentially select for use 0.15: 1～0.6: 1.
Adding an amount of ligand the 4th component water in the catalyzer, is key character of the present invention, and it can improve activity of such catalysts, thinks with traditional spectators, and water is that the poisonous substance of Ziegler-type catalyst is completely different, and this is our beyond thought new discovery.We find, water is when content is very low in raw material, and catalyst activity is very low, and along with water-content increases, catalyst activity is along with raising, and after content acquired a certain degree, catalyst activity began again to descend.The suitable scope H2O mole number/transition metal carboxylate salt mole ratio of the content of water in catalyst system is 1.8: 1～3.9: 1.
Water is in catalyst system, suitable content can improve activity of such catalysts, exact mechanism the present invention inquires into, but but preliminary interpretation is: water is a kind of hard base, it can stable molecule hydrogen heterolytic fission produces on complex catalyst proton, promoted the activation of molecular hydrogen, and molecular hydrogen activation, the prerequisite of hydrogenation just.Yet water-content is too high, can destroy the aluminum alkyls in the catalyzer again too much, makes active decline, and even disappears.At this moment, water becomes the poisonous substance of catalyzer again.
In the catalyst system, the adding of the 4th component water must be in synergistic effect under the 3rd component weak organic acid coupling, and catalyzer just has more obvious improvement.
In the example below, the marked improvement of this invention obtains detailed illustrating.In the example 1,2,3, homogeneous catalyst is formulated by the first component Primary Catalysts and the second component promotor.Example 4 increases the 3rd component, and example 5 preparations have the 4th component, in example 6 to 17 homogeneous catalysts, both have been furnished with the 3rd component, are furnished with the 4th component again, compare with example 1,2,3, and catalyst reaction speed is obviously accelerated, and extend reaction time widely.
The preparation method of homogeneous catalyst of the present invention generally can be undertaken by following step.At normal temperatures and pressures, at first the 4th component water is joined in the cyclohexane solution of transition metal carboxylate salt, make the transition metal carboxylate salt by the 4th component water saturation, then the trialkyl aluminum solutions is added among the transition metal carboxylic acid salt solution, add the 3rd component alcohols at last.
The preparation of used transition metal carboxylate salt, be that carboxylic acid and sodium hydroxide with C6～C18 carries out saponification, generate carboxylic acid sodium salt, need not be through washing, then in the carboxylic acid sodium salt aqueous solution that generates, the aqueous solution that adds the transition metal inorganic salt, carry out replacement(metathesis)reaction, then, under dry and filtration situation, add cyclohexane solvent, the transition metal carboxylate salt that generates is extracted.In extraction process, finish the preparation of transition metal carboxylate salt cyclohexane solution simultaneously and in the transition metal carboxylic acid salt solution, add two technological processs of the 4th component water.Adopt the distinguishing feature of above-mentioned technological process to be, the transition metal carboxylate salt of being produced can obtain higher yield, generally can reach more than 90%, and this is in the prior art, the fresh content of never reporting.
Four components of homogeneous catalyst, the addition sequence in the complexing preparation process is not the key of preparation catalyzer.As the transition metal carboxylic acid salt solution of Primary Catalysts first component, can add earlier in the trialkyl aluminum solutions, same trialkyl aluminum solutions also can add earlier among the transition metal carboxylic acid salt solution.As the alcohols of weak organic acid, can add earlier among the transition metal carboxylic acid salt solution, also can at first add in the trialkyl aluminum solutions, also can in the homogeneous catalyst preparation process, add at last.The 4th component water can add earlier among the transition metal carboxylic acid salt solution or in the last adding of catalyst preparation process.
Example 1, be solvent, prepare triethyl aluminum and nickel octoate solution respectively with the hexanaphthene.Again with triethyl aluminium solution with the AL/Ni(atomic ratio) equal in the goat's horn bottle that 4.0 amount adds 200 milliliters, adding content then is the nickel octoate solution of 2.07 gram nickel octoates, and makes homogeneous catalyst.800 milliliters of benzene feedstock are added in the reactor, add in succession as the above-mentioned homogeneous catalyst of producing, at 180 ℃ and 7Kg/Cm
2The hydrogen branch is depressed and is carried out benzene hydrogenation, reacts and no longer inhales hydrogen after 70 minutes.The transformation efficiency of benzene is more than 99.7%, and the purity of hexanaphthene is more than 99.7%.Proceed continuous hydrogenation on this basis, the reaction time of evaluate catalysts, it is 20 hours that the purity of hexanaphthene is reduced to reaction times of 95% by 99.7%.(also can be described as life of catalyst the reaction time of catalyzer).
Example 2, be solvent, prepare triethyl aluminium solution and nickel naphthenate solution respectively with the hexanaphthene.Again with triethyl aluminium solution with the AL/Ni(atomic ratio) equal 4.0 amount and add in the 200ml goat's horn bottle, be concentration that the nickel naphthenate solution 11.6ml of 0.0302 gram Ni/ml adds in the goat's horn bottle then, make homogeneous catalyst.The 800ml benzene feedstock is added in the reactor, add in succession as the above-mentioned homogeneous catalyst of making, at 180 ℃ and 7Kg/Cm
2The hydrogen branch is depressed and is carried out benzene hydrogenation, reacts and no longer inhales hydrogen after 72 minutes, and the transformation efficiency of benzene is more than 99.7%, and the purity of hexanaphthene is more than 99.7%.Proceed continuous hydrogenation reaction on this basis, the reaction time of evaluate catalysts, it is 22 hours (also can be described as life of catalyst the reaction time of catalyzer) that the purity of hexanaphthene is reduced to reaction times of 95% by 99.7%.
Example 3, be solvent, prepare triethyl aluminium solution and isocaprylic acid nickel solution respectively with the hexanaphthene.Again with triethyl aluminium solution, with the AL/Ni(atomic ratio) equal 4.0 amount and add in the 200ml goat's horn bottle, with the amount of 2.07 gram isocaprylic acid nickel, add the isocaprylic acid nickel solution then, make homogeneous catalyst.The 800ml benzene feedstock is added in the reactor, add in succession as the above-mentioned homogeneous catalyst of making, at 180 ℃ and 7Kg/Cm
2The hydrogen branch is depressed and is carried out benzene hydrogenation, after reaction is carried out 69 minutes, no longer absorbs hydrogen, and the transformation efficiency of benzene hydrogenation is more than 99.7%, and the purity of hexanaphthene is more than 99.7%.Proceed the continuous hydrogenation reaction on this basis, the reaction time of evaluate catalysts, the purity of hexanaphthene reduces to 95% by 99.7%, and the reaction times is 21 hours (also can be described as life of catalyst the reaction time of catalyzer).
Example 4, with example 3 same procedure bases on, the amount that equals 0.24 with the ratio of isooctyl alcohol mole number/nickel salt mole number adds the 3rd component isooctyl alcohol in addition, makes homogeneous catalyst.Carry out benzene hydrogenation with example 3 identical reaction conditionss, after reaction is carried out 70 minutes, no longer absorb hydrogen, the transformation efficiency of benzene hydrogenation is more than 99.7%, and the purity of hexanaphthene is more than 99.7%.Proceed the continuous hydrogenation reaction on this basis, the reaction time of evaluate catalysts, the purity of hexanaphthene reduces to 95% by 99.7%, and be 120 hours (catalyst life) reaction time.Compare with example 1,2,3, owing to add the 3rd component, rise appreciably reaction time, but the initial action velocity variations is little.
Example 5, be solvent, prepare triethyl aluminium solution and isocaprylic acid nickel solution respectively with the hexanaphthene.Again the 4th component water is added in the isocaprylic acid nickel solution, it is reached capacity.With the AL/Ni(atomic ratio) equal 4.0 amounts of calculating triethyl aluminums, get the triethyl aluminium solution that has prepared, add in the goat's horn bottle, and then adding contains the isocaprylic acid nickel solution (amounts that wherein contain the 4th component water that isocaprylic acid nickel amount is 2.07 grams, equaling 2.75 with H20/ isocaprylic acid nickel mol ratio calculates), make homogeneous catalyst.The 800ml benzene feedstock is added in the reactor, add in succession as the above-mentioned homogeneous catalyst of making, at 180 ℃ and 7Kg/Cm
2The hydrogen branch is depressed and is carried out benzene hydrogenation, after reaction was carried out 30 minutes, no longer absorbs hydrogen, and the transformation efficiency of benzene is more than 99.7%, and the purity of hexanaphthene is more than 99.7%.Proceed continuous hydrogenation reaction on this basis, the reaction time of evaluate catalysts, it is 23 hours (be also referred to as life of catalyst the reaction time of catalyzer) that the purity of hexanaphthene is reduced to reaction times of 95% by 99.7%.Compare with example 1,2,3,4,, initial action speed is accelerated greatly, but do not have reaction time (life-span) example 4 long owing to add the 4th component water.
Example 6, preparation of catalysts are on example 5 bases, are that 0.24 amount adds the 3rd component isooctyl alcohol with isooctyl alcohol/isocaprylic acid nickel (mol ratio), make homogeneous catalyst.The 800ml benzene feedstock is added in the reactor, add in succession as the above-mentioned homogeneous catalyst of making, at 180 ℃ and 7Kg/Cm
2The hydrogen branch is depressed and is carried out benzene hydrogenation, after reaction is carried out 27 minutes, no longer absorbs hydrogen, and the transformation efficiency of benzene is more than 99.7%, and the purity of hexanaphthene is more than 99.7%.Proceed continuous hydrogenation reaction on this basis, the reaction time of evaluate catalysts, it is 208 hours (be also referred to as life of catalyst the reaction time of catalyzer) that the purity of hexanaphthene is reduced to reaction times of 95% by 99.7%.This example is compared with example 5 owing to add the synergistic effect of pure and mild the 4th component water of the 3rd component simultaneously, has both improved catalyzer initial action speed, has improved life of catalyst again greatly.
Example 7, on the method basis of example 6 preparation catalyzer, changing the reductive agent triethyl aluminum is aluminium isobutyl, makes homogeneous catalyst.Use-case 6 similarity conditions and method are carried out the benzene hydrogenation test, and catalyzer initial action speed is 29 minutes, and be 160 hours reaction time (life-span).
Example 8, replace outside the isocaprylic acid nickel divided by the 2 ethyl hexanoic acid cobalt, other condition, method and the example 6 of preparation catalyzer are identical, and the AL/CO atomic ratio equals 5.5, is made into homogeneous catalyst.Use-case 6 same quadrat methods are carried out the benzene hydrogenation test, and catalyzer initial action speed is 30 minutes, and be 170 hours reaction time (life-span).
Example 9, replace outside the isocaprylic acid nickel divided by capric acid nickel, all the other and identical with method time of the condition of example 6 are made into homogeneous catalyst.Use-case 6 same quadrat methods are carried out the benzene hydrogenation test, and catalyzer initial action speed is 29 minutes, and be 164 hours reaction time (life-span).
Example 10, replace outside the isocaprylic acid nickel divided by nickel stearate, all the other and identical with method time of the condition of example 6 are made into homogeneous catalyst.Use-case 6 same quadrat methods are carried out the benzene hydrogenation test, and catalyzer initial action speed is 32 minutes, and be 125 hours reaction time (life-span).
Example 11, replace outside the 3rd component isooctyl alcohol divided by 3-ethyl octanol-(3), all the other and identical with method time of the condition of example 6 are made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 28 minutes, and be 188 hours reaction time (life-span).
Example 12, replace outside the 3rd component isooctyl alcohol divided by the trimethyl carbinol, all the other are identical with method down with the condition of example 6, are made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 29 minutes, and be 175 hours reaction time (life-span).
Example 13, except that changing the AL/NI atomic ratio, all the other and identical with method time of the condition of example 6, the AL/NI atomic ratio is 5.0, is made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 38 minutes, and be 140 hours reaction time (life-span).
Example 14, except that changing the AL/NI atomic ratio, all the other and identical with method time of the condition of example 6, the AL/NI atomic ratio is 2.5, is made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 41 minutes, and be 135 hours reaction time (life-span).
Example 15, except that the mol ratio that changes isooctyl alcohol/transition metal carboxylate salt, all the other are identical with the condition and the method for example 6, isooctyl alcohol/isocaprylic acid nickel mol ratio is 0.18, is made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 29 minutes, and be 169 hours reaction time (life-span).
Example 16, except that the mol ratio that changes isooctyl alcohol/transition metal carboxylate salt, all the other are identical with the condition and the method for example 6, isooctyl alcohol/isocaprylic acid nickel mol ratio is 5.0, is made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 30 minutes, and be 172 hours reaction time (life-span).
Example 17, remove to change H
2Outside the mol ratio of O/ isocaprylic acid nickel, all the other are identical with the condition and the method for example 6, H
2O/ isocaprylic acid nickel mol ratio is 1.90, is made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 48 minutes, and be 170 hours reaction time (life-span).
Example 18, remove to change H
2Outside the mol ratio of O/ isocaprylic acid nickel, all the other are identical with the condition and the method for example 6, H
2O/ isocaprylic acid nickel mol ratio is 3.05, is made into homogeneous catalyst.Use-case 6 carries out the benzene hydrogenation test with quadrat method and condition, and catalyzer initial action speed is 27 minutes, and be 155 hours reaction time (life-span).
Claims (3)
1, a kind of benzene hydrogenating homogeneous catalyst, its reactive metal is selected transiting metal nickel or cobalt for use, preferentially select metallic nickel for use, the negatively charged ion of compound is the carboxylate radical of C6～C8, with trialkyl aluminium is promotor, molecular formula is ALR1R2R3, R1 wherein, R2, R3 is respectively C1～C16 alkyl, it is characterized in that: selecting weak organic acid for use is catalyzer the 3rd component, select four component of water for use as catalyzer, triethyl aluminum and transition metal carboxylate salt mole ratio are 1: 1～8: 1, and weak organic acid and transition metal carboxylate salt mole ratio are 0.1: 1～1: 1, and water and transition metal carboxylate salt mole ratio are 1.8: 1～3.9: 1.
2, benzene hydrogenating homogeneous catalyst according to claim 1 is characterized in that the best proportioning of weak organic acid and transition metal carboxylate salt mole number is 0.15: 1～0.6: 1.
3, benzene hydrogenating homogeneous catalyst according to claim 1, the optimum mole ratio that it is characterized in that triethyl aluminum and transition metal carboxylate salt is 2: 1～5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88105065A CN1012814B (en) | 1988-05-21 | 1988-05-21 | Homogeneous catalyst of benzene hydrogenization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88105065A CN1012814B (en) | 1988-05-21 | 1988-05-21 | Homogeneous catalyst of benzene hydrogenization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1037729A CN1037729A (en) | 1989-12-06 |
| CN1012814B true CN1012814B (en) | 1991-06-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88105065A Expired CN1012814B (en) | 1988-05-21 | 1988-05-21 | Homogeneous catalyst of benzene hydrogenization |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2716190B1 (en) * | 1994-02-17 | 1996-04-12 | Inst Francais Du Petrole | Hydrogenation catalyst and process for the hydrogenation of benzene using said catalyst. |
| CN1082388C (en) * | 1997-09-05 | 2002-04-10 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| CN1079291C (en) * | 1998-09-16 | 2002-02-20 | 巴陵石油化工公司鹰山石油化工厂 | Method for prolonging service life of benzene hydrogenation homogeneous catalyst |
| CN1094386C (en) * | 2000-06-08 | 2002-11-20 | 复旦大学 | Non-crystal catalyst for hydrogenating benzene and its preparing process |
| CN101289365B (en) * | 2008-06-03 | 2011-10-05 | 北京大学 | Low-temperature catalytic benzene hydrogenation method and special catalyst thereof |
| CN105646142B (en) * | 2014-12-02 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of method for being catalyzed ester through hydrogenation alcohol |
| CN111085269B (en) * | 2018-10-24 | 2023-03-14 | 中国石油化工股份有限公司 | Hydrogenation catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and hydrogenation method thereof |
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1988
- 1988-05-21 CN CN88105065A patent/CN1012814B/en not_active Expired
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| CN1037729A (en) | 1989-12-06 |
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