CN1249291A - Process for producing cycloolefine - Google Patents

Process for producing cycloolefine Download PDF

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CN1249291A
CN1249291A CN98124139A CN98124139A CN1249291A CN 1249291 A CN1249291 A CN 1249291A CN 98124139 A CN98124139 A CN 98124139A CN 98124139 A CN98124139 A CN 98124139A CN 1249291 A CN1249291 A CN 1249291A
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catalyst
ruthenium
water
catalyst slurry
sulfuric acid
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CN1159269C (en
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芦田启太
岩崎峰征
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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Priority to JP04956498A priority Critical patent/JP4025411B2/en
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Priority to CNB981241395A priority patent/CN1159269C/en
Priority to DE19845283A priority patent/DE19845283B4/en
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

A process for preparing cycloolefin features that in the presence of catalyst slurry containing metal Ru catalyst, water and metallic sulfate, the mononuclear aromatics is partially hydrogenated by hydrogen, and includes a step to control the activity of catalyst. Said step features that when the water phase where said catalyst exists has a pH value from 2.5 to 7.0 measured at ordinary temp and pressure, adding alkaline compound to the catalyst slurry can decrease the activity of catalyst and adding sulfuric acid to it can increase its activity. Said addition can take place during or before reaction.

Description

Produce the method for cycloolefin
The present invention relates to a kind of method of producing cycloolefin, promptly have lower section hydrogenation mononuclear aromatics at ruthenium catalyst.
Cycloolefin, especially tetrahydrobenzene compound are the valuable intermediates of organic chemical industry's product, especially are used as the raw material of polymeric amide and Methionin.
The various methods of known production cycloolefin, in these methods, the most frequently used in the presence of ruthenium catalyst the partial hydrogenation by mononuclear aromatics, for improving selectivity and productive rate, study, and a lot of result of study second is appeared in the newspapers and is led to many kinds of catalyst components and carrier, metal-salt are used for reaction system etc. as additive.
For example, reaction system is proposed the suggestion which follows, water and zinc coexist as in the reaction system, and can produce cycloolefin with quite high productive rate thus.
(1) a kind of method with hydrogen partial reduction mononuclear aromatics, in the presence of water and at least a zn cpds, under neutrality or acidic conditions, carry out this method with beaded catalyst, wherein catalyzer mainly contains metal Ru, and ruthenium has average crystallite size 30 to 200 and by carrier band [JP-B-8-25919 (using term " JP-B " to refer to " Japanese patent laid-open publication gazette of having examined ")] on carrier herein.
(2) a kind of method of in the presence of ruthenium catalyst, producing cycloolefin by the partial hydrogenation mononuclear aromatics, wherein, in reaction system, under complete dissolved state, there be (JP-B-5-12331) at least a zinc oxide and zinc hydroxide with the amount that is not more than saturation solubility.
(3) a kind of in the presence of water with the method for hydrogen partial reduction mononuclear aromatics; wherein; in the presence of at least a solid alkaline zinc; under neutrality or acidic conditions; use oxidation catalyst particles to carry out this reaction, described granules of catalyst mainly contains and has average crystallite size 200 or lower metal Ru (JP-B-8-19012).
In the presence of water and zinc sulfate, use ruthenium catalyst, by producing in the method for cycloolefin with hydrogen partial reduction mononuclear aromatics, aspect reaction effect, after deliberation add the effect of sulfuric acid or basic cpd.The result shows, even when adding sulfuric acid, the performance change of catalyzer is very little, adds the selectivity (APPlied Catalysis A:General, 89 (1992) 77～102) that basic cpd causes reactivity to reduce and improved cycloolefin.
Also known, at aqueous phase, in the presence of water and at least a water-soluble zinc compound, under acidic conditions, in by method with hydrogen partial reduction mononuclear aromatics production cycloolefin, add the sulfuric acid utmost point and be effective in the increase speed of reaction, wherein, the catalyzer of carrier band does not contain the metal Ru by the preparation of reduction ruthenium compound, this ruthenium compound contains zn cpds, in ruthenium heavily is base, and zinc content is 0.1～50%, and use has average crystallite size and is not more than 200 as hydrogenation catalyst (JP-B-2-16736).
Producing in the industrial practice of cycloolefin method by using hydrogen partial hydrogenation mononuclear aromatics with ruthenium catalyst, if can be, so, can not change the amount of catalyst reactor and change output by simple method control catalyst activity, perhaps, can remedy the reduction of catalyst activity in time.Can finish the change of catalyst activity by changing temperature of reaction or pressure, still, the variation of these conditions needs that heat extraction equipment is arranged in the reactor, perhaps controls the hydrogen compressed step in the equipment of industrial product again.These methods need many times and cost, therefore do not wish so.
In addition, the method that changes catalyst activity is reversible preferably, if catalyst activity can not modulation, disadvantageously, so the catalyst activity that changes can not turn back to original valence state.This causes the increase of catalyst system therefor amount or productive rate to reduce.Therefore, this method reversible as far as possible preferably.In other words, need a kind of like this method, wherein,, still can turn back to required original valence state though the catalytic activity of catalyzer repeatedly changes or raises and reduce.
A kind of so needed method can easily be made a kind of like this method, and it comprises, discharges catalyzer or catalyzer is added to the output that changes cycloolefin in the reactive system by part from reactive system.Yet,, therefore be difficult for carrying out these operations because this reactive system has high temperature and high pressure.For example, change 20% cycloolefin output if desired, so, need put into or take out the catalyzer of reaction system, its amount is 20% of catalytic amount in the reactive system.If when it was used to produce per year the industrial continuous production equipment that is not less than 10000 tons of cycloolefins, the amount of catalyst slurry reached the amount of kiloton to thousands of tons of at least in the reactive system, and it 20% also is very huge.In order to put into and take out the catalyst slurry of reactive system huge amount like this, need to consider especially security at least.In addition, production unit must be too in large scale.And, if when producing cycloolefin, put into and take out the catalyzer of reactive system, cause the change of catalyst slurry liquid measure in the reactive system, cause in the reactor variation of oil and catalyst slurry ratio, cause in the reactive system very turbulence.For making this confusion controlled also is very bothersome.Still often can make this confusion controlled anything but at an easy rate.Therefore, this method may be the reality and the practical methods of producing cycloolefin hardly.
As mentioned above, as the method that reduces or increase catalyst activity, advised never that any simple method can put into practice in specific and technical scale.In addition, do not advise the method for the industry needs of modulation catalyst activity.And the selection of not advising promptly not influencing cycloolefin can change the method for catalyst activity again.
An object of the present invention is to provide a kind of preparation method of high efficiency production cycloolefin, this method can be eliminated prior art and produce open question in the cycloolefin method.
Other purpose of the present invention and effect will become more obvious by following description.
In the presence of ruthenium catalyst, water and metal sulfate,, keep a close eye on activity of such catalysts producing in the method for cycloolefin with hydrogen partial hydrogenation Polycyclic aromatic hydrocarbons.Inventor's broad research how to reduce or improve catalyst activity or repeat to change catalyst activity.As a result, found a kind of method of producing cycloolefin, this method can be finished above-mentioned purpose of the present invention, and does not produce very little or not influence to the selectivity of cycloolefin or productive rate.Finished the present invention thus.
By providing following method to realize above-mentioned purpose of the present invention.
(1) method of production cycloolefin, this method is in the presence of the catalyst slurry that contains ruthenium catalyst, water and metal sulfate, by carrying out with hydrogen partial hydrogenation mononuclear aromatics, comprises the active step of control catalyst.
(2) according to the method for above-mentioned (1), wherein said control comprises, when normal temperature and normal pressure measurement, the pH value of the water of catalyzer existence therein is being not less than 2.5 to the condition that is lower than in 7.0 scopes, by add the step that basic cpd reduces catalytic activity in catalyst slurry.
(3) according to the method for above-mentioned (1), wherein said control comprises, when normal temperature and normal pressure measurement, the pH value of the water of catalyzer existence therein is being not less than 2.5 to the condition that is lower than in 7.0 scopes, by add the step that sulfuric acid increases catalytic activity in catalyst slurry.
(4) according to the method for above-mentioned (2), wherein said control also comprises, when normal temperature and normal pressure measurement, the pH value of the water of catalyzer existence therein is being not less than 2.5 to the condition that is lower than in 7.0 scopes, by add the step that sulfuric acid increases catalytic activity in catalyst slurry.
(5) in the presence of the catalyst slurry that contains ruthenium catalyst, water and metal sulfate, by the method for producing cycloolefin with hydrogen partial hydrogenation mononuclear aromatics, wherein, when normal temperature and normal pressure measurement, the pH value of the water of catalyzer existence therein is not less than 2.5 to the condition that is lower than in 7.0 scopes, changes the catalytic activity of described catalyst slurry before hydrogenation by at least a basic cpd of interpolation and sulfuric acid in catalyst slurry.
(6) according to the method for above-mentioned (5), wherein reversibly change catalytic activity.
(7) according to each method of claim 1 to 6, wherein, the catalyst slurry that contains ruthenium catalyst, water and metal sulfate in nitrogen atmosphere, kept 24 hours with high temperature and high pressure or the longer time after, carry out the interpolation of described sulfuric acid and/or basic cpd.
(8), wherein, be that the catalyst slurry that is using in the reaction is carried out the interpolation of described sulfuric acid and/or basic cpd according to each method of above-mentioned (1) to (7).
(9), wherein, be to carrying out the interpolation of described sulfuric acid and/or basic cpd with forming eddy current round-robin catalyst slurry according to each method of above-mentioned (1) to (8).
(10) according to each method of above-mentioned (1) to (9), wherein, be that the pipeline that flows through catalyzer that is circulated to reactor by water-and-oil separator is carried out the interpolation of described sulfuric acid and/or basic cpd.
(11) according to the method for above-mentioned (10), wherein the total amount catalyst slurry that exists in not being shorter than circulation and reactive system is measured the interpolation of carrying out described sulfuric acid and/or basic cpd in time of catalyst slurry required time equally.
(12) according to each method of above-mentioned (1) to (11), wherein said basic cpd is the basic salt with the metallographic phase metal of the same type that constitutes described metal sulfate.
(13) according to each method of above-mentioned (1) to (12), wherein said basic cpd is oxyhydroxide or the oxide compound with the metallographic phase metal of the same type that constitutes described metal sulfate, the complexing salt of perhaps described metallic compound and metal sulfate.
(14) according to each method of above-mentioned (1) to (13), wherein said metal sulfate is a zinc sulfate.
(15) according to each method of above-mentioned (1) to (14), the amount of wherein said metal sulfate is 1 * 10 of a water weight -5To 1.0 times.
(16) according to each method of above-mentioned (1) to (15), wherein the amount of water is heavy 0.5 to 20 times of described mononuclear aromatics.
(17) according to each method of above-mentioned (1) to (16), wherein said ruthenium catalyst comprises the metal Ru that is obtained by the reduction ruthenium compound.
(18) according to the method for above-mentioned (17), wherein said ruthenium catalyst comes the catalyzer of carrier band and contains to have the metal Ru that average crystallite size does not lie in 200 .
(19) according to the method for above-mentioned (17) or (18), wherein ruthenium compound contains zn cpds, and based on the weight of ruthenium, the content of zinc is 0.1 to 50% (weight).
The invention still further relates to a kind of method of catalytic activity of control catalyst slurries, this method is to use described catalyst slurry in by the method for producing cycloolefin with hydrogen partial hydrogenation mononuclear aromatics, described catalyst slurry contains ruthenium catalyst, water and metal sulfate, and this method comprises one of following at least step:
Add basic cpd to catalyst slurry; With
Add sulfuric acid to catalyst slurry,
Described interpolation is to carry out under such condition, and when normal temperature and normal pressure measurement, the pH value of the water of catalyzer existence therein is not less than 2.5 to being lower than in 7.0 scopes.
Fig. 1 is diagram shows relation between reaction times and the benzene transformation efficiency in the experiment 1,2 and 3 of embodiment 1;
Fig. 2 is diagram shows relation between reaction times and the benzene transformation efficiency in the experiment 1,2 and 3 of embodiment 2;
Fig. 3 is diagram shows relation between benzene transformation efficiency and the tetrahydrobenzene selectivity in the experiment 1,2 and 3 of embodiment 2;
Fig. 4 is diagram shows relation between reaction times and the benzene transformation efficiency in the enforcement 1,2 and 3 of embodiment 3; With
Fig. 5 is that diagram shows concerns between benzene transformation efficiency and the tetrahydrobenzene selectivity in the experiment 1,2 and 3 of embodiment 3.
Below the present invention will be described in more detail.
Mononuclear aromatics as raw material is the aromatic hydrocarbons with a phenyl ring in the present invention.The example of aromatic hydrocarbons comprises benzene like this, toluene, dimethylbenzene and the benzene that is replaced by the alkyl that generally has 1 to 4 carbon atom.
The ruthenium catalyst of Shi Yonging is a kind of catalyzer that comprises by the metal Ru of pre-reduction ruthenium compound preparation in the present invention.The example of ruthenium compound comprises its halogenide such as muriate, bromide and iodide like this, nitrate, vitriol, oxyhydroxide, with the various ruthenium complexs that contain, as the ruthenium carbonyl complex compound, the methyl ethyl diketone ruthenium complex, the ruthenocene complex compound, amine ruthenium complex and by such complex compound derived compounds.These ruthenium compounds can be used as its two or more mixture and use.The example of method of reduction ruthenium compound comprise reduce with contacting of hydrogen, carbon monoxide etc. and with the chemical reduction of formalin, sodium borohydride, hydrazine etc.Preferably contact reduction in these methods with hydrogen.Generally can be 50 to 450 ℃, preferred 100 to 400 ℃ and realize this contact reduction in temperature.If reduction temperature is lower than 50 ℃, the time that reduction needs is too many.On the contrary,, may cause promoting the ruthenium agglomeration of particles, cause active or disadvantageous effect optionally if reduction temperature surpasses 450 ℃.Not only can but also can contact reduction, but preferably in liquid phase, carry out in gas phase in liquid phase.This is because reduction makes it can remove the impurity that dissolves in the water that uses in liquid-phase reduction in liquid phase.If impurity enters reactive system, generally they have adverse influence to reaction, for example, reduce the selectivity and the catalytic activity of cycloolefin.
As the ruthenium catalyst that uses among the present invention, the preferred reductive ruthenium catalyst that uses by above-mentioned reduction method preparation is to improve the selectivity of the cycloolefin of producing thus.
Can also use the catalyzer that mainly contains ruthenium among the present invention, it is by adding another kind of metal or metallic compound prepares to ruthenium compound before or after ruthenium compound reduction.The example of metal and metallic compound comprises zinc, chromium, molybdenum, tungsten, manganese, cobalt, nickel, iron, copper, gold, the compound of palladium and these metals.When using these metals or metallic compound, its atomic ratio to ruthenium atom generally is preferably 0.001 to 20.Zn cpds preferably in these metals and the metallide.Preferably before the ruthenium compound reduction, zinc and zn cpds are added in this ruthenium compound, so that the highly selective of cycloolefin to be provided.Based on the weight of ruthenium, treat that the amount of zincification or zn cpds is preferably 0.1 to 50% (weight) especially.The example of these zn cpdss comprises zinc hydroxide, zinc oxide, zinc chloride, zinc nitrate and zinc sulfate.
The ruthenium catalyst of Shi Yonging can be by carrier band on carrier in the present invention.Carrier is not particularly limited.The example of carrier comprises metal, as magnesium, aluminium, silicon, ruthenium, titanium, vanadium, chromium, manganese, cobalt, iron, nickel, copper, zinc, zirconium, hafnium and tungsten, the oxide compound of these metals, composite oxides, oxyhydroxide, vitriol, different water-soluble salts and two or more chemistry or the physical bond compound and the mixture that form by these carriers.The example of the method for carrier band ruthenium comprises absorption, ion-exchange, dipping, co-precipitation, drying and spraying on these carriers.Based on vehicle weight, the carrier band amount of ruthenium is preferably 0.001-20% (weight).If the carrier band amount of ruthenium is too little, need a large amount of carriers, on the contrary, if ruthenium carrier band amount is too big, the ruthenium particle is assembled, and reduces the metallic surface active site, makes the not enough branch of catalyzed reaction aborning.
Yet, preferably, use ruthenium catalyst, rather than carrier band is on carrier, so that produce higher cycloolefin selectivity with the form of granular metal ruthenium.In the case, the average crystallite size of metal Ru preferably is not more than 200 .If the average crystallite size of metal Ru surpasses 200 , minimizing is present in the lip-deep active site of ruthenium catalyst, reduce catalytic activity, and therefore may need to use a large amount of ruthenium catalysts.
In reactive system of the present invention, must have water.Although it is different according to reaction type,, 0.001 to 100 times of weight of the preferably used mononuclear aromatics raw material weight of institute's water consumption.If institute's water consumption is too little, cause the selectivity of cycloolefin to descend, on the contrary, if water consumption is too big, it is unfavorable to cause, the reactor bigger as needs.Therefore, preferably, the water yield that exists in reactive system is 0.5 to 20 times of weight of used mononuclear aromatics raw material weight.
Yet, in any case, need the amount of water should be enough to prevent aqueous liquid phase and contain the raw material organic phase and under reaction conditions, be mixed into one mutually mutually with main component product.In other words, the amount of water should be enough to keep a kind of like this state, and the organic liquid phase that promptly mainly contains raw material and product is that oil phase is separated from each other with containing the water of water as major ingredient, that is to say that the two-phase of oil phase and water is simultaneous.Main ingredient used herein is meant the component with maximum mol ratio that constitutes each liquid phase component.
In reactive system, coexist, the hydrogen ion concentration of the aqueous phase that forms by water, promptly PH preferably is lower than 7.0, and is promptly acid.
In addition, in the present invention, need the existence of metal sulfate.In reactive system, special requirement all the metal sulfates of amount do not exist with solid, still, it is existing under dissolution conditions to small part of amount all.The example that is present in the metal of aqueous phase as metal sulfate comprises zinc, iron, nickel, cadmium, gallium, plugs with molten metal, magnesium, aluminium, chromium, manganese, cobalt and copper.Can mix two or more that use these metal sulfates.And, can also use the two salt that contain such metal sulfate.For obtaining the highly selective of cycloolefin, zinc sulfate is preferred especially the use.Although the kind according to metal sulfate is different,, the amount of used metal sulfate is preferably 1.0 * 10 -5To 1.0 times of water weight that in reactive system, exist.If make metal sulfate with zinc sulfate, the amount of zinc sulfate is preferably greater than 1.0 * 10 -4To 0.5 times of water weight that in reactive system, exists.
Following metal sulfate may reside in the reactive system of the present invention.The example of these metal-salts comprises nitrate, muriate, oxide compound, oxyhydroxide, acetate and the phosphoric acid salt of metal, and such metal is selected from: element weekly form 1 family's metal, as lithium, sodium and potassium; The metal of 2 families is as magnesium and ruthenium (family's number is according to IUPAC Nomenclature of Inorganic Chemistry, Revised Edition (1989)); With zinc, manganese, cobalt, copper, cadmium, copper, arsenic, iron, gallium, germanium, vanadium, chromium, silver, gold, platinum, nickel, palladium, barium, aluminium or the like.Can also chemistry and/or physical mixed and use two or more these metal-salts.In these metal-salts, preferably zinc salt such as zinc hydroxide and zinc oxide are added in the reactive system, especially, preferably in reactive system, have the two salt that contain zinc hydroxide, for example by general formula (ZnSO 4) m (Zn (OH) 2) those of n (wherein m: n=1: 0.01 to 1: 100) expression.
In the present invention, there is no particular limitation for the amount of used metal-salt, as long as when under specified temperature and pressure, measuring, the pH value of water remain on be not less than 2.5 be lower than 7.0.Yet, in fact, be generally 1 * 10 of used ruthenium weight -5To 1 * 10 5Times weight.These salt may reside in reactive system Anywhere, there is no need to require it all to measure and separate in aqueous phase.
Outside dewatering, one or more organic substances with one or more hydroxyls may reside in the reactive system.Yet, when this organic substance can be dissolved in water and comprise the cycloolefin raw material and by the organism of its deutero-cycloolefin and naphthenic hydrocarbon in the time, preferred amount of regulating the organic substance of this hydroxyl is so that make in reactive system water and oil phase not mix mutually to form single-phase.That is to say that the addition of described organic substance makes reaction liquid constitute two different phases, i.e. water and oil phase preferably in such scope.
One of the present invention is characterised in that the control catalytic activity.
In one embodiment of the invention, in the control catalytic activity, react.
In another embodiment of the invention, use catalyst slurry to react with preliminary control catalytic activity.
Preferably carry out the control of catalytic activity: reduce catalytic activity by in catalyst slurry, adding basic cpd by at least one step; When measuring gage fixed temperature and specified pressure, be not less than 2.5 to the condition that is lower than 7.0 scopes at the PH of water, improve catalytic activity by in catalyst slurry, adding sulfuric acid.
Further key character of the present invention is to use method of the present invention can reversibly change catalytic activity.
The modulation of catalytic activity used herein refers to and repeatedly improves and reduce catalytic activity.In other words, improve catalytic activity if desired, need in reaction system, add sulfuric acid.On the contrary, reduce catalytic activity if desired, can in reactive system, add basic cpd.Thus, when needs, can increase or suppress catalytic activity.
More specifically, the modulation of catalytic activity used herein refers to, and when needs, the specific activity with 1.0 value catalyzer can repeatedly be reduced to and be lower than 1.0, is elevated to greater than 1.0 and turn back to 1.0.
The reason that can change catalytic activity in the present invention is, neutralizes with sulfuric acid because institute adds basic cpd, in fact, mainly due to the existence of basic cpd, reduces significantly or eliminated the toxicity on the catalyzer.Therefore, if with zinc oxide as basic cpd, it is such that the ideal of catalyst activity changes, the specific activity of catalyst system, its original specific activity is 1, it mixes with 0.1 mole of zinc oxide, has 0.7 specific activity, be greater than 0.7 to less than 1 when mixing, when mixing with 0.05 mol sulfuric acid again, turn back to 1 again with 0.05 mol sulfuric acid.In fact, the relation between reaction times and benzene transformation efficiency replaces in the specific activity, and the experimental result in the contrast can be understood this phenomenon better.
Yet only because this phenomenon of pH value of water will never occur, wherein the aqueous phase ruthenium catalyst changes and exists or water is to be neutralized.This point also can be by such fact proved, when under the nitrogen atmosphere with high temperature and high pressure ruthenium catalyst being kept with the catalyst slurry form, its performance changes in time, makes interpolation sulfuric acid or basic cpd be difficult to the selectivity generation effect of cycloolefin.In other words, this also can be understood by such fact, when used 24 hours or the longer time be exposed to the high temperature and high pressure nitrogen atmosphere contain the catalyst slurry of ruthenium catalyst, water and metal sulfate the time, add sulfuric acid or basic cpd the selectivity of cycloolefin produced slight influence.
The inventor infers, owing to being maintained at the following time of nitrogen atmosphere with high temperature and high pressure when ruthenium catalyst with water and metal sulfate, near the metal sulfate or derivatives thereof that exists ruthenium catalyst is subjected to changing and therefore changing for the susceptibility of adding sulfuric acid or basic cpd as the time spent at ruthenium catalyst.
Yet, surprisingly, traditional knowledge, promptly under acidic conditions, in the presence of ruthenium catalyst, water and vitriol, add sulfuric acid to very little effect being arranged with hydrogen partial hydrogenation mononuclear aromatics, what this knowledge and the inventor set forth in this article is above-mentioned content with one's lot diverse.According to traditional knowledge, it is insignificant adding sulfuric acid.Therefore, the absolute unexpected inventor of traditional knowledge is described in this article increases the phenomenon of catalyst activity by adding sulfuric acid.The inventor infers that this difference is very different owing to adding sulfuric acid amount.In the present invention, the vitriolic addition is very little, must be, the aqueous phase under specified temperature and pressure, the pH value of catalyst slurry is being not less than 2.5 to being lower than in 7.0 scopes.On the contrary, in traditional knowledge, reach 2.4 up to ph value of aqueous phase and just add sulfuric acid.
Another conventional knowledge, i.e. knowledge described in JP-B-2-16736, it is extremely effective to improving speed of response to add sulfuric acid, only, as the influence to reaction result, adds the increase that sulfuric acid provides speed of response.In addition, the patent of quoting as proof does not above relate to and advises about adding sulfuric acid even the catalyst reaction course being had reversible or irreversible effect.Therefore, can not expect the present invention who makes by the inventor fully easily from the above-mentioned patent of quoting as proof by the reversible change sign of catalyst activity.
In the present invention, if use sulfuric acid, sulfuric acid preferably is added in the catalyst slurry that contains ruthenium catalyst, water and metal sulfate, these slurries keep and are exposed in the nitrogen atmosphere with high temperature and high pressure 24 hours or longer.This is because remained in the nitrogen atmosphere with High Temperature High Pressure 24 hours or the catalyst slurry of longer time presents the raising of catalytic activity, and when mixing with sulfuric acid, cycloolefin is optionally influenced very little or insensitivity.In addition, more preferably use and in having the nitrogen atmosphere of High Temperature High Pressure, kept 100 hours or the longer time catalyst slurry, this be because, even further increase the multiplicity of sulfuric acid and basic cpd, also almost can not give the reversibility of catalytic activity and the selection performance of alkene is produced minimum influence.
Under High Temperature High Pressure, keep catalyst slurry to refer to, under preferred 110 to 160 ℃ and pressure 1 to 100 normal atmosphere, preferred 20 to 29 normal atmosphere catalyst slurry is exposed in the nitrogen atmosphere 100 to 200 ℃ of temperature.If temperature or pressure are lower than the above-mentioned range of definition, the time that in fact will cost a lot of money produces the required effect that produces when catalyst slurry is remained on High Temperature High Pressure.On the contrary, if temperature or pressure surpass the scope of above-mentioned definition, to generation injurious effects such as activity of such catalysts.Therefore, temperature and pressure preferably drops in the scope of above-mentioned definition.
And, if in having the nitrogen atmosphere of High Temperature High Pressure, keep the time of catalyst slurry too short, by under high temperature and high pressure, keeping the effect that catalyzer produced insufficient.Therefore, the time that in having the nitrogen atmosphere of High Temperature High Pressure, keeps catalyst slurry preferably 24 hours or longer time, more preferably 100 hours or longer time.
For making reaction conditions drop on above-mentioned scope, can be implemented in the operation that keeps catalyzer under the nitrogen atmosphere with high temperature and high pressure simultaneously at production cycloolefin generation hydrogenant.In other words, the present invention can be used for being not less than 24 hours for the production cycloolefin has reacted, and preferably is not less than 100 hours catalyst slurry.
In the present invention, if in reaction system can not ignore big amount, follow by obvious big multiple by the accumulation of these additive or derivatives thereofs and to repeat to add sulfuric acid and/or basic cpd, catalyst slurry may partly stand quiescent setting, generation contains the supernatant liquid of these additives and derivative, substituted by water then, make it can suppress the accumulation that these materials exceed needs.Yet, when adding basic cpd, can use the basic salt of these metals, for example be formed in the metal sulfate that reaction system Central Plains pre-exists, form the oxide compound or the oxyhydroxide of such metal with double salt by such compound and metal sulfate.Then, with sulfuric acid these salt that neutralize, get back to the metal sulfate of the type, it is original a large amount of existence in the reaction system.In addition, when discharging product from reactor, the mixing of these metal sulfates or the form that is dissolved in the product (as cycloolefin) are discharged from reactive system slightly.Therefore, on industrial level, the accumulation and the other problem of said derivative can not take place generally.
In the present invention, sulfuric acid and basic cpd can add in the reactive system at the same time or separately.If add this two kinds of additives simultaneously, note the molar ratio separately of sulfuric acid to be added and basic cpd.In other words, improve catalytic activity if desired, must add two kinds of additives with such mol ratio, even so that two kinds of additives mix, and mutual neutralization also will keep excess sulfuric acid in reactive system, on the contrary, suppresses catalytic activity if desired.Must add two kinds of catalyzer with such mol ratio, even so that two kinds of additives mix, and mutual neutralization also will keep the excessive of basic cpd in reactive system.From the viewpoint of purpose of control catalytic activity, preferably add two kinds of additives respectively, to produce higher efficient at different positions.In other words, can be by the reaction of adding the gas washing in SA production cycloolefin succeeded by producing the reaction of cycloolefin by adding basic cpd.Depend on the circumstances, add the order of two kinds of additives and can put upside down.In addition, need not require alternative ground to add sulfuric acid and basic cpd.When needs change catalytic activity, can add sulfuric acid or basic cpd with aequum.The interpolation of these additives is not carried out in the reaction of breaks in production cycloolefin.
The term of Shi Yonging " basic cpd " means such compound in this article, at normal temperatures and pressures, in argon atmospher, when mixing with aqueous sulfuric acid, with 1N aqueous sulfuric acid reaction generate water at least and or the compound of hydrogen molecule, perhaps, under the reaction conditions of producing cycloolefin, change the compound that forms with the correlated alkali of sulfuric acid.
The former comprises by the example of compound: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Ga, Al, Y, Mo, Ag, Cd, In, Sn, Cr; The oxyhydroxide of these metals, oxide compound carbon, hydrochlorate and supercarbonate; The double salt that contains at least a these metals, oxyhydroxide, oxide compound, carbonate and supercarbonate.Especially, on industrial level, more wish, because its effect is rapidly with tangible by the oxyhydroxide or the oxide compound that enrich raw material energy mass-producted be easy to get alkali-metal or zinc.
The example of latter's compound comprises: metal is nitrate, ammonium salt, organic acid salt, vanadate, germanate, chromic salt, dichromate, phosphoric acid salt, manganate, selenate, selenite, arsenate, nitride and the trinitride of Li, Na, K, Rb, Cs, Be, Mg, Zn, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Ga, Al, Y, Mo, Ag, Cd, In, Sn and Cr for example; Contain the organic complex of such metal, particularly contain amino, diazo, cyano group or analogue nitrogenous complex compound as ligand as central metal; Nitrogenous organic materials, for example nitric acid, ammonia, methylamine and each seed amino acid.
Yet, if the contained metal of basic cpd is different with the metal of unborn formation metal sulfate in reactive system, even use nitrogen or carbon on a small quantity, these additives or be accumulated in the reactive system by its derived compounds, in order to suppress this phenomenon, can preferably use in the above-mentioned basic cpd and the basic salt that constitutes unborn metal sulfate same metal in the reaction system, the especially double salt that forms by such compound metal vitriol.If use the basic cpd of the type,,, in reactive system, only cause metal vitriolic amount to improve so that mainly generate metal sulfate with the sulfuric acid neutralization that is added in the reactive system.With compare in the amount of the unborn metal sulfate of reactive system, the sulfuric acid that is added and the amount of alkaline metal salt are minimum, therefore, can ignore the raising of the amount of metal sulfate in the reactive system substantially.
If use zinc sulfate as metal sulfate, so, with the basic salt that is formed in the metal sulfate same metal that reactive system Central Plains pre-exists, especially the double salt that forms by such compound and metal sulfate, be Alkaline Zinc, zinc oxide especially, zinc hydroxide or by general formula (ZnSO 4) m (Zn (OH) 2) the represented double salt of n, m in the formula: n be 1: 0.01 to 100.If use ruthenium sulfate as metal sulfate, so, it is alkaline ruthenium, ruthenium oxide especially, hydroxide ruthenium or by general formula (CdSO 4) m (Cd (OH) 2) double salt of n institute tabular form, m in the formula: n be 1: 0.01 to 100.
Can use basic cpd of the present invention with the form of hydrate.In addition, can be with basic cpd with water or wait to be fed to the mononuclear aromatics in the reactive system or be fed in the reactive system with the form of mixtures of the metal sulfate aqueous solution.
As sulfuric acid to be used in the present invention, can be not less than the commercial vitriol oil of 95% (weight) according to the form working concentration of former state or dilute with water.Alternatively, can be lower than the commercial dilute sulphuric acid of 95% (weight) according to the form working concentration that former state or water further dilute.In addition, can use and have equal in quality (purity, foreign matter content, etc.).The sulfuric acid in these commercial products for example.Can use the sulfuric acid that contains minute quantity impurity, described impurity generally all contains in commercial product.For example, Fe, Cl, Cu, Pb, As and Se.Yet, preferably use guaranteed reagent,G.R. level or higher levels of sulfuric acid.
Among the present invention, sulfuric acid and/or basic cpd can be added in the liquid phase or gas phase in the reactive system.Yet preferably, these additives are added in the liquid phase.Especially, when catalyzer contains ruthenium catalyst, water and metal sulfate liquid stream, always can these additives be added in the liquid phase with the well-mixed position of whole catalyst slurry in the reactive system, so that make the effect of sulfuric acid and/or basic cpd act on catalyzer as far as possible equably thus at them.For example, preferably be agitating vane can reach in the reactor stirring power position or these additives are added in the liquid phase round-robin position all the time in catalysis.
If sulfuric acid and/or basic cpd just are added in the catalyst for reaction slurries, can intermittently or add continuously.If intermittently add sulfuric acid and/or basic cpd, advantage is, before and after adding, can adjust the effect that interpolation produced by these additives by the analytical results of product, but shortcoming is that the unexpected variation of catalytic activity causes turbulent flow in reactive system.If add continuously, shortcoming is be not easy to control at once by the interpolation effect that these additives produced, but advantage to be that reactive system is stable.Therefore.According to the method for control reaction result, can suitably determine the adding mode of these additives.
Yet if intermittently add sulfuric acid and/or basic cpd, preferably spending some times adds these additives, so that the catalyzer in the reactive system is produced uniform additive effect.The interpolation time is depended on the amount of ruthenium catalyst in the reactive system or the addition of sulfuric acid and/or basic cpd to a great extent.Yet, in the practice, once add preferred with about 1 second to 24 hours.
In addition, sulfuric acid and/or basic cpd are being added to just under the situation of catalyst for reaction slurries, when catalyzer near temperature of reaction, promptly temperature is high when being not less than 50 ℃, must pay special attention to.This be because, to be in temperature high to the catalyst slurry that is not less than 50 ℃ if sulfuric acid and/or basic cpd are added to, formation reaction generation too quickly may all act on catalyst slurry near these additive positions of interpolation.This reduces the effect of adding sulfuric acid and/or basic cpd probably significantly.
Pay special attention to, at first preferably, form the turbulent position at catalyst slurry stream sulfuric acid and/or basic cpd are added in the reactive system.The temperature of catalyst slurry is high more, add sulfuric acid and/or basic cpd rapid more to the effect of catalyst slurry, the diffusion of these additives in whole additive may be difficult more.Therefore, preferably be in full mobile position, more preferably add these additives in the turbulent flow position at catalyst slurry.Used in this article term " turbulent flow " refers to have and is not less than 4000 state as the Reynolds number that defines in the chemical engineering.
The second, except first described attention, preferably, add these additives in catalyst slurry round-robin position, make the additive effect of these additives act on whole catalyst slurries more equably.For example, by water-and-oil separator catalyst slurry is being separated from the oil plant that contains mononuclear aromatics and its reaction product, then with under the anti-also situation in the reactor of isolating catalyzer like this, sulfuric acid and/or basic cpd can be fed to through its catalyzer and be recycled to the pipeline of reactor from water-and-oil separator.
The 3rd, in second attention, importantly, carry out the interpolation of sulfuric acid and/or basic cpd, so that the additive effect of these additives acts on whole catalyst slurries more equably with time enough.This is because if the interpolation time is short, these additives can only act on the catalyzer of the pipeline of just flowing through, and make it be difficult to reach effect of uniform.About adding the required further preferred time, the whole catalyzer that exist in reactive system are through pipeline cycle period, and the interpolation time preferably is not less than same amount catalyst slurry required time.If the problem of catalyst slurry is that the cycle rate of 1000ml and catalyst slurry is per minute 200ml in the reactive system, preferably with 5 minutes or longer time interpolation sulfuric acid and/or basic cpd.
Sulfuric acid and/or the basic cpd situation in the catalyst for reaction slurries just of being added to compared with the situation in the catalyzer that these additives is added to ongoing reaction not to be shown, preferably additive is added to just in the catalyst for reaction slurries in the present invention.The reason of this suggestion is that the catalyst slurry of ongoing reaction shows rapidlyer the additive effect of additive to just comparing not at the catalyst for reaction slurries like this, makes it can regulate each time amount to be added.If additive is added in the catalyst slurry of ongoing reaction not like this, unless make the catalyst slurry reaction, this needs extra operation, otherwise, can not accurately control the additive effect of such additive.For example, if add such additive of inaccurate amount, make reaction uncertain.The term of Shi Yonging " just at the catalyst for reaction slurries " refers to the catalyst slurry that exists under the reaction conditions of producing cycloolefin in this article.
In the present invention, before reaction beginning, by in reactive system, adding an amount of sulfuric acid and/or the basic cpd catalytic activity when can conditioned reaction beginning in advance.Yet as mentioned above, maximum feature of the present invention is, by promptly just add sulfuric acid and/or basic cpd can suppress or improve catalytic activity at the catalyst for reaction slurries after causing.Further feature of the present invention is can reversibly control catalytic activity by repeating this process.Particularly, under the situation of reacting with continuous processing, application of the present invention can change catalyst activity at any time and need not rest production unit, and can reversibly repeat this process.Therefore, with change cycloolefin output or change temperature of reaction or other condition identical, can change catalyst activity and not change the amount of catalyzer in the reactive system, can overcome the variation of above-mentioned cycloolefin output.In addition, according to the present invention, in changing the catalytic activity procedure, need from reactive system, not discharge catalyst slurry especially and then it is handled as cleaning.Therefore can not produce refuse.The method of production cycloolefin of the present invention not only can be used for rhythmic reaction technology but also can be used for continuous reaction process.Yet, in fact, be preferred for continuous reaction process.
As detailed above, open question is a utmost point otherwise effective technique in the prior art for solving in the present invention.This technology always can not produced cycloolefin effectively on industrial level.Therefore, the present invention is a technology of starting the New Times.
Described herein " normal temperature and normal pressure " is meant 20 ℃ and 1 normal atmosphere.
In order to measure the average crystallite size of ruthenium catalyst, only obtain the stretching, extension of diffracted ray width by the x-ray diffraction of catalyst system therefor, rein in (Scherrer) Equation for Calculating quite at length by the west, use Cuk αRay is as the X-radiant.Then, have the maximum diffraction line width by near the diffraction angle 44 ℃ (2 θ) and stretch the average crystallite size of calculating ruthenium catalyst.
With reference to following embodiment the present invention is described in more detail, but can not be interpreted as limitation of the present invention.
Based on experimental result, calculate the cyclohexene selectivity of listing in following embodiment and the comparative example by following equation:
Tetrahydrobenzene selectivity (%)
=(the tetrahydrobenzene mole number that reaction generates/p) * 100
P (mole number)=(the cyclohexene mole number that generates by reaction)+(the cyclohexane mole number that generates by reaction) wherein
Based on experimental result, by the transformation efficiency of following Equation for Calculating benzene:
The benzene transformation efficiency
=(by the mole number of the benzene of reaction consumes) * 100/ (being fed to the mole number of benzene in the reactor)
Embodiment 1 Preparation of catalysts
Carry out Preparation of catalysts by following method
Mix 50g ruthenium chloride (RuCl 33H 2O) 130g zinc chloride and 5.0L 1N hydrochloric acid.In mixture, add 1.0L 30% (weight) salt acid sodium aqueous solution then at once.After this mixture was stirred 2 hours at 70 to 90 ℃.This relief mixture cooling is also left standstill.Remove the supernatant liquor that generates again.Remove the black precipitate that generates through filter paper filtering.The black precipitate that to so remove is sent in the 1L beaker then.Be purpose, add 500ml 1N aqueous sodium hydroxide solution to throw out with alkaline aqueous solution washing and precipitating thing.In room temperature mixture was stirred 1 hour.After stirring end, allow mixture staticly settle, remove the supernatant liquid of generation then.After this by extract the throw out that generates through filter paper filtering.This alkalescence is cleaned triplicate.Obtain the main black precipitate that constitutes by the hydroxide ruthenium that contains zinc hydroxide thus.In 5% (weight) aqueous sodium hydroxide solution, disperse so to obtain black precipitate then.The liquid that again public affairs loose joins its internal surface of 1L internal volume and has used in the teflon-coating autoclave.With the air in the hydrogen displacement autoclave.Under nitrogen atmosphere, 50 normal atmosphere and 150 ℃ and under stirring with material reduction 36 hours.Allow material cool off again, the pressure of autoclave is got back to the normal pressure value.Extract the black precipitate that generates by filter paper filtering.The black precipitate that to remove is thus delivered in the 1L flask again.For with alkaline aqueous solution washing and precipitating thing, 500ml 30% (weight) sodium hydroxide solution is added in the throw out, stirred the mixture at normal temperatures then 1 hour, stirring allows mixture staticly settle after finishing, and removes the upper strata of generation again and cleans.By extract the throw out that generates through filter paper filtering.Repeating five this alkalescence cleans.Clean identical method again with throw out flushing 10 times with above-mentioned alkalescence, different is that water replaces 30% (weight) aqueous sodium hydroxide solution.The throw out vacuum-drying that to so clean then obtains 18g black ruthenium catalyzer.So the zinc content of the ruthenium catalyst that obtains is 5.3% (weight) (average crystallite size: about 59 ).Experiment 1
1.5g is so obtained ruthenium catalyst, 7.5g as the zirconium white of dispersion agent (average crystallite size: about 200 ), 280ml normal-temperature water and 49g ZnSO 47H 2Its internal surface that O (by Wako Pure chemicalIndustries, the guaranteed reagent,G.R. that Ltd. produces) is added to the 1L internal volume scribbles in the high still as reactor of tetrafluoroethylene.Thoroughly replace gas in the autoclave with hydrogen then.Closed reaction vessel airtightly again.Use the electromagnetic induction paddling process, the temperature with reaction vessel in the catalyst slurry that high-speed stirring so adds is raised to 130 ℃.In reaction vessel, add High Pressure Hydrogen again, reach 50 normal atmosphere up to wherein pressure.After this, infeeded 10ml water with 10 minutes in the clockwise reaction vessel by the high-voltage device pump.So finish the interpolation of water.In autoclave, be pressed into 130 ℃ of liquid benzene of 140ml then at once, be 50 normal atmosphere and 130 ℃ and high-speed stirring and be pressed under the condition of hydrogen in reaction pressure, allow reaction mixture react during reaction, from autoclave, extract the part reaction soln with proper spacing, check oil ingredient by gas-chromatography.Experiment 2
Experiment 1 identical method with embodiment 1 experimentizes, and different is, will make solution that 10ml obtains with high-pressure pump by dilute with water 10mg sulfuric acid in 10 minutes and be added to catalyst slurry in the reaction vessel and add and substitute 10ml water.Experiment 3
Reclaim used reaction soln in the experiment 2, so the reaction soln that reclaims does not contain organism fully.Reclaim catalyst slurry then fully.After this, its internal surface that the catalyst slurry that so reclaims is joined the 1L internal volume scribbles in the autoclave as reaction vessel of tetrafluoroethylene.Thoroughly replace gas in the autoclave, hermetic closed again reactor with hydrogen then.Use the electromagnetic induction paddling process, the temperature with reaction vessel in the catalyst slurry that high-speed stirring so adds is raised to 130 ℃.In reaction vessel, add High Pressure Hydrogen again, reach 50 normal atmosphere up to wherein pressure.After this, will be added in the reaction vessel with 10ml water with the zinc oxide of sulfuric acid equimolecular quantity that embodiment 2 adds with 10 minutes by high-pressure pump.So finish the interpolation of water.In autoclave, add 130 ℃ of liquid benzene of 140ml at once.Then, be 50 normal atmosphere and 130 ℃ and high-speed stirring and be pressed under the condition of hydrogen, allow reaction mixture react, during reaction, from autoclave, extracts the part reaction soln, by gas-chromatography inspection oil ingredient with proper spacing in reaction pressure.
In the experiment 1 to 3 of embodiment 1,, promptly under oil phase and water existence condition, react two kinds of liquid phases.Before and after reaction, the pH value of catalyst slurry is being not less than 2.5 to being lower than 7.0 under normal temperature and normal pressure.
Experiment 1 to 3 comparison shows that with respect to the original value before the interpolation sulfuric acid, adding sulfuric acid provides the increase of catalyst activity and add the reduction that zinc oxide provides catalytic activity subsequently among the embodiment 1.In other words, can reversibly change catalytic activity.Experiment 2 shows that when the benzene transformation efficiency was identical in these experiments, during evaluation, high several percentage points tetrahydrobenzene selectivity was lower than the selectivity of experiment 1 and 3.
Embodiment 2 experiments 1
With the ruthenium catalyst that 1.5g is obtained by the operation (Preparation of Catalyst) of embodiment 1,7.5g as the zirconium white of dispersion agent (average crystallite size: about 200 ), 280ml normal-temperature water and 49g ZnSO 47H 2Its internal surface that O (producing guaranteed reagent,G.R. by WakoPure chemical industry company limited) is added to the 1L internal volume scribbles in the autoclave as reaction vessel of tetrafluoroethylene.After the hermetic closed reaction vessel, thoroughly replace gas in the autoclave with hydrogen again.Use the magneticinduction paddling process, the temperature with reaction vessel in the catalyst slurry that high-speed stirring so adds is raised to 130 ℃.In reaction vessel, add High Pressure Hydrogen again, reach 50 normal atmosphere up to wherein pressure.Under these conditions, promptly under 130 ℃ and 50 atmospheric nitrogen atmosphere, under the condition of high-speed stirring, after pressurising finishes reaction vessel was kept 24 hours.After this, in 10 minutes, in reaction vessel, infeed 10ml water, so finish the interpolation of water by high-pressure pump.In autoclave, be pressed into 130 ℃ of liquid benzene of 140ml at once.Be 50 normal atmosphere and 130 ℃ and high-speed stirring and be pressed under the condition of hydrogen in reaction pressure then, allow reaction mixture react.During reaction, from autoclave, extract part solution, by gas-chromatography check oil ingredient with proper spacing.Experiment 2
Experimentize with experiment 1 identical method among the embodiment 2, different is, adds dilute with water 10mg sulfuric acid in the catalyst slurry in reaction vessel through high-pressure pump in 10 minutes and makes the solution of 10ml and substitute 10ml water.Experiment 3
Reclaim anticaustic reaction soln in the experiment 2, so the reaction soln that reclaims does not contain organism fully.Reclaim catalyst slurry then fully.After this, its internal surface that the catalyst slurry that so reclaims is added to the 1L internal volume scribbles in the autoclave as reaction vessel of tetrafluoroethylene, thoroughly replaces gas in the autoclave, the airtight again reaction vessel that closes with hydrogen then.Use the electromagnetic induction paddling process, the temperature with reaction vessel in the catalyst slurry that high-speed stirring so adds is raised to 130 ℃.In reaction vessel, add High Pressure Hydrogen again, reach 50 normal atmosphere up to wherein pressure.After this, will test 2 zinc oxide that add the sulfuric acid equimolecular quantity by high-pressure pump in 10 minutes in embodiment 2 is added in the reactor with 10ml water.So finish the interpolation of water.In autoclave, add 130 ℃ of liquid benzene of 140ml at once.Then, be 50 normal atmosphere and 130 ℃ and high-speed stirring and be pressed under the condition of hydrogen, allow reaction mixture react in reaction pressure.During reaction, from autoclave, extract the part reaction soln, by gas-chromatography check oil ingredient with appropriate intervals.
In the experiment 1 to 3 of embodiment 2,, promptly under oil phase and water existence condition, react two kinds of liquid phases.In under keeping having the nitrogen atmosphere condition of High Temperature High Pressure, in reaction vessel, thoroughly stir catalyst slurry.Before and after reaction, the pH value of catalyst slurry is not less than 2.5 to being lower than 7.0 under normal temperature and normal pressure.
Experiment 1 to 3 comparison shows that with respect to the original value before the interpolation sulfuric acid, adding sulfuric acid provides the catalyst activity raising and add the reduction that zinc oxide provides catalytic activity subsequently among the embodiment 2.In other words, can reversibly change catalytic activity.In addition, after these operations, the tetrahydrobenzene selectivity presents very little or does not change.
Embodiment 3 Preparation of catalysts
Carry out the process (Preparation of Catalyst) of embodiment 1, different is not use zinc chloride.Therefore, the pre-reduction ruthenium compound obtains 15g ruthenium catalyst (crystallite dimension: 56 ).Experiment 1
0.5g is come from the ruthenium catalyst that 15g so obtains, 280ml normal-temperature water and 49g ZnSO 47H 2Its internal surface that o (by the guaranteed reagent,G.R. of WaKo Pure chemical industry company limited production) is added to the 1L internal volume scribbles in the autoclave as reaction vessel of tetrafluoroethylene.Thoroughly replace gas in the autoclave, hermetic closed again reaction vessel with hydrogen.Use the magneticinduction paddling process, the temperature with reaction vessel in the catalyst slurry that high-speed stirring so adds is raised to 150 ℃.In reaction vessel, add High Pressure Hydrogen again, reach 50 normal atmosphere up to wherein pressure.Under these conditions, promptly under 150 ℃ and 50 atmospheric nitrogen atmosphere, under the condition of high-speed stirring, after pressurising finishes reaction vessel was kept 24 hours.After this, in 10 minutes, in reaction vessel, infeed 10ml water, so finish the interpolation of water by high-pressure pump.In autoclave, be pressed into 150 ℃ of liquid benzene of 140ml at once.Then, be that 50 normal atmosphere and 130 ℃ and high-speed stirring are pressed under the condition of hydrogen at reversed stress, allow reaction mixture react.During reaction, from autoclave, extract part solution, by gas-chromatography check oil ingredient with appropriate intervals.Experiment 2
Experimentize with experiment 1 identical method among the embodiment 3, different is, substitutes 10ml water in high-pressure pump will be made 10ml by dilute with water 5mg sulfuric acid in 10 minutes solution is added to catalyst slurry in the reactor.Experiment 3
Reclaim the used reaction soln of experiment 2 of embodiment 3, so the reaction soln that reclaims does not contain organism fully.Reclaim catalyst slurry then fully.After this, its internal surface that the catalyst slurry that so reclaims is added to the 1L internal volume scribbles in the autoclave as reaction vessel of tetrafluoroethylene, thoroughly replaces gas in the autoclave, hermetic closed again reaction vessel with hydrogen then.Use the electromagnetic induction paddling process, the temperature with reaction vessel in the catalyst slurry that high-speed stirring so adds is raised to 150 ℃.In reaction vessel, add High Pressure Hydrogen again, reach 50 normal atmosphere up to wherein pressure.After this, the zinc oxide that 2 of the experiments of embodiment 3 is added the sulfuric acid equimolecular quantity by high-pressure pump in 10 minutes is added in the reactor with 10ml water, so finishes the interpolation of water.In autoclave, add 150 ℃ of liquid benzene of 140ml at once, then, be 50 normal atmosphere and 130 ℃ and high-speed stirring and be pressed under the condition of hydrogen, allow reaction mixture react in reaction pressure.During reaction, from autoclave, extract the part reaction soln, by gas-chromatography check oil ingredient with proper spacing.
In the experiment 1 to 3 of embodiment 3,, promptly under the condition of oil phase and water existence, react two kinds of liquid phases.In under keeping having the nitrogen atmosphere of High Temperature High Pressure, in reactor, thoroughly stir catalyst slurry.Before and after reaction, the pH value of catalyst slurry is not less than 2.5 to being lower than 7.0 under normal temperature and normal pressure.Used zinc oxide in the experiment 3 of used sulfuric acid and embodiment 3 in the experiment 2 as embodiment 3, use be guaranteed reagent-grade product available from Wako Pure chemical industry company limited.
Experiment 1 to 3 comparison shows that among the embodiment 3, and with respect to the original value before the interpolation sulfuric acid, interpolation sulfuric acid provides catalyst activity to increase and adds zinc oxide subsequently provides catalytic activity to reduce.In other words, can reversibly change catalytic activity.In addition, after these operations, the tetrahydrobenzene selectivity presents very little variation or does not change.
Embodiment 4
When benzene being infeeded continuously in 3 liters of internal volume reactors, therefrom discharge the catalyst slurry that in reactor, exists continuously and by benzene, the oil that tetrahydrobenzene and hexanaphthene constitute with the form of mixture d.Then, the mixture of so discharging is added in the water-and-oil separator, catalyst slurry is separated mutually with oil phase.Isolating catalyst slurry like this is looped back reactor.Like this, oil is discharged separately.Use this experimental installation, carry out following experiment.
At first, 5.0g is come from the ruthenium catalyst that 18g obtains in embodiment 1,30g as the zirconium white of dispersion agent (average crystallite size: about 200 ), 2000ml normal-temperature water and 400g ZnSO 47H 2O (by the guaranteed reagent,G.R. of Wako Pure chemistry company limited production) is added in the reactor.With the gas in the thorough metathesis reactor of hydrogen.Promote the pressure and temperature in the reactor then.Use high-speed stirring, beginning is fed to the benzene under the normal temperature in the reactor with 1500ml/ hour speed.Depress at 150 ℃ of temperature of reaction and 50 atmospheric pressure hydrogens and to carry out successive reaction.To be not less than the reaction aequum hydrogen is fed in the reactor.Excessive hydrogen is removed from reactor through the gas phase position.Catalyst slurry of discharging continuously from reactor and oil are separated from each other in water-and-oil separator.Isolating catalyst slurry like this is circulated back in the reactor with set rate continuously through recycle pump.During reaction, with this quadrat method control water yield in reactive system to be added, promptly in the reactor liquid phase volume keep constant be reactor, water-and-oil separator, recycle pump at reactive system with pipeline that these equipment link to each other in the amount of urging agent liquid that exists constant.Treat to be recycled to from water-and-oil separator the amount of the catalyst slurry of reactor, promptly 10 times of volumes of amount of predetermined catalyst slurry are in the amount of waiting to be fed to the benzene in the reactor.The temperature of waiting to infeed catalyzer is 150 ℃.Speed with solution form water to be discharged from reactive system in oil is not less than every little 10ml.With with the common identical amount water post-reactor of discharging of benzene.
When reaction beginning after 250 hours the time,, in 1 hour, will be fed in the reactive system by alkene sulfuric acid with the acquisition of 5ml water dilution 5.0mg sulfuric acid at the catalyst slurry circulation line place between catalyst slurry recycle pump drain position and reactor.During this process, the water yield that infeeds with benzene is to deduct the value that institute's water content obtains in dilute sulphuric acid from preset value.After 2 hours, to mix with 5ml water with the zinc oxide of 5.0mg sulfuric acid equimolar amount.Then, the catalyst slurry circulation line place between catalyst slurry recycle pump drain position and reactor in 1 hour, is fed to this mixture in the reactive system.After this, amounted to 8 times with per 2 hours with above-mentioned identical method, comprise be added on for the first time in, add sulfuric acid or zinc oxide.
The first interpolation after the sulfuric acid, the benzene amount that joins in the reactor so changes, and promptly keeps the benzene transformation efficiency of discharge reactive system constant.When needing, suitably the oil of being discharged from reactive system at experimental session by the check of gas phase gas-chromatography is formed.Carry out other analysis at predetermined interval.Specifically, analyzed earlier in preceding 1 hour beginning to add sulfuric acid.After this, analyzed for totally 9 times in per 2 hours.So obtain evaluating data.
In this embodiment, two kinds of liquid phases, promptly react under the condition of oil and water existence, catalyst slurry connects catalyst slurry recycle pump drain position at pipeline and flows to reactor with turbulent flow.In addition, the pH value of catalyst slurry is being not less than 2.5 to being lower than in 7.0 scopes at normal temperatures and pressures.As the sulfuric acid that uses in the present embodiment, use be guaranteed reagent-grade product available from Wako Pure chemical industry company limited.
1 to, 9 analytical results among the embodiment 4; (sulfuric acid or zinc oxide, the benzene conversion ratio cyclohexene that the output that benzene amount that the unit time infeeds and hexamethylene are rare all illustrates in following table 1 additive types before near the analysis. analysis times analysis was not long ago added select (ml/h) (mol/h) 1 one 41.4 73.7 1,500 5.16 2 sulfuric acid 41.3 73.6 1,595 5.46 3 zinc oxide 41.4 73.7 1,498 5.15 4 sulfuric acid 41.2 73.9 1,589 5.45 5 sulfuric acid 41.3 73.8 1,675 5.75 6 zinc oxide 41.3 73.7 1,590 5.45 7 sulfuric acid 41.4 73.6 1,679 5.76 8 zinc oxide 41.3 73.7 1,596 5.47 9 zinc oxide 41.3 73.8 1,505 5.17 of selecting property of output sequence number additive types (%) (%) of the infeed amount cyclohexene of benzene
The result of embodiment 4 shows, adds sulfuric acid and zinc oxide in being exposed to 250 hours catalyst slurry of High Temperature High Pressure hydrogen, can reversibly change catalytic activity at the cycloolefin production period, and is in this process, very little to the selectivity influence of cycloolefin.
As above-mentioned, produce following unusual effect in invention:
1) according to the present invention, in producing the cycloolefin method, if need to increase or reduce the situation of output, the appropriate amount that only passes through at the appropriate time to catalyst slurry add sulfuric acid and/or when basic cpd can be easily and promptly increase or reduce output.
2) in the present invention, under normal temperature and normal pressure, be not less than 2.5 in the pH value that described catalyzer is present in liquid phase wherein and realizing adding sulfuric acid and/or basic cpd to catalyst slurry in being lower than 7.0 scopes, so, basic cpd and vitriolic addition are very little.
3) therefore, during these additives add, do not need to change significantly the operational condition of the whole technology of producing cycloolefin.
4), add the reversibly activity of control catalyst of sulfuric acid and/or basic cpd to catalyst slurry according to the present invention.
5) therefore, at any time can overcome the change that also repeats the output that takes place, and, can reduce because the reduction of catalytic activity and the amount of the catalyzer that replenishes to reactive system.
6) as noted above, according to the present invention, can overcome the increase or the reduction of cyclenes output by open-and-shut equipment and operation, and, can produce cycloolefin effectively by the utmost point.
Although invention has been described in detail and with reference to its specific embodiment,, obviously to those skilled in the art, can make different changes and improvements not breaking away under the spirit and scope of the present invention situation.

Claims (29)

1, a kind of method of producing cycloolefin, this method is in the presence of the catalyst slurry that contains ruthenium catalyst, water and metal sulfate, carries out with hydrogen partial hydrogenation mononuclear aromatics, comprising the active step of control catalyst.
2, according to the method for claim 1, wherein said control comprises, when normal temperature and pressure was measured, the pH value that is present in water wherein at catalyzer was not less than 2.5 to the condition that is lower than in 7.0 scopes, by adding the step that basic cpd reduces catalytic activity to catalyst slurry.
3, according to the method for claim 1, wherein said control comprises, when normal temperature and pressure is measured, be not less than under 2.5 the conditions to low 7.0 scopes, by adding the step that sulfuric acid improves catalyst activity to catalyst slurry at the pH value that catalyzer is present in water wherein.
4, according to the method for claim 2, wherein said control also comprises, when normal temperature and pressure was measured, the pH value that is present in water wherein at catalyzer was not less than 2.5 to the condition that is lower than in 7.0 scopes, by adding the step that sulfuric acid improves catalyst activity to catalyst slurry.
5, a kind of method of producing cycloolefin, in the presence of the catalyst slurry that contains ruthenium catalyst, water and metal sulfate, by carrying out this method with hydrogen partial hydrogenation mononuclear aromatics, wherein, when normal temperature and pressure is measured, the pH value that is present in water wherein at catalyzer is not less than 2.5 to the condition that is lower than in 7.0 scopes, before hydrogenation by add the catalytic activity that at least a basic cpd and sulfuric acid change described catalyst slurry to catalyst slurry.
6, according to the method for claim 5, wherein department changes catalytic activity contraryly.
7, according to each method of claim 1 to 6, wherein, the catalyst slurry that contains ruthenium catalyst, water and metal sulfate in nitrogen atmosphere, kept 24 hours with high temperature and high pressure or the longer time after, carry out the interpolation of described sulfuric acid and/or basic cpd.
8,, wherein be that the catalyst slurry that is using in the reaction is carried out the interpolation of described sulfuric acid and/or basic cpd according to the method for claim 7.
9, method according to Claim 8 wherein is to carry out the interpolation of described sulfuric acid and/or basic cpd to forming turbulent flow round-robin catalyst slurry.
10,, wherein be that the pipeline that flows through catalyst slurry that is circulated to reactor by water-and-oil separator is implemented described interpolation according to the method for claim 9.
11, according to the method for claim 10, wherein carry out the interpolation of described sulfuric acid and/or basic cpd in the time of the catalyst slurry required time of the same amount of the catalyst slurry total amount that in not being shorter than circulation and reactive system, exists.
12, according to the method for claim 7, wherein said basic cpd is the basic salt with the metallographic phase that constitutes described metal sulfate metal of the same type.
13, according to the method for claim 12, wherein said basic cpd is oxyhydroxide or the oxide compound with the metallographic phase metal of the same type that constitutes described metal sulfate, the binding substances of perhaps described metallic compound and metal sulfate.
14, according to the method for claim 7, wherein said metal sulfate is a zinc sulfate.
15, according to claim 14 method, the amount of wherein said metal sulfate is 1 of water weight * 10-5 to 1.0 times.
16, according to the method for claim 7, wherein the amount of water is 0.5 to 20 times of described mononuclear aromatics weight.
17, according to the method for claim 11, wherein said ruthenium catalyst comprises by reduction ruthenium compound acquisition metal Ru.
18, according to the method for claim 17, wherein said ruthenium catalyst is that the catalyzer of not carrier band and containing has the metal Ru that average crystallite cun chi is not more than 200 .
19, according to the method for claim 18, wherein ruthenium compound contains zn cpds, and based on the weight of ruthenium, the content of zinc is 0.1 to 50% (weight).
20, a kind of method of catalytic activity of control catalyst slurries, this method is to use described catalyst slurry in by the method for producing cycloolefin with hydrogen partial hydrogenation mononuclear aromatics, this catalyst slurry contains ruthenium catalyst, water and metal sulfate, and this method comprises one of following at least step:
When normal temperature and pressure was measured, the pH value of the water of catalyzer existence therein was not less than 2.5 to the condition that is lower than in 7.0 scopes,
Add the alkalify thing to catalyst slurry; With
Add sulfuric acid to catalyst slurry.
21, according to the method for claim 13, wherein said ruthenium catalyst contains by reduction ruthenium compound acquisition metal Ru.
22, according to the method for claim 21, wherein said ruthenium catalyst is the catalyzer of not carrier band and contains and have average crystallite size and be not more than 200 metal Ru.
23, according to the method for claim 22, wherein ruthenium compound contains zn cpds, and based on the weight of ruthenium, the content of zinc is 0.1 to 50% (weight).
24, according to the method for claim 15, wherein said ruthenium catalyst contains the metal Ru that is obtained by the reduction ruthenium compound.
25, according to the method for claim 24, wherein said ruthenium catalyst is the catalyzer of not carrier band and contains and have average crystallite size and be not more than 200 metal Ru.
26, according to the method for claim 25, wherein ruthenium compound contains zn cpds, based on the weight of ruthenium, the content of zinc be 0.1 to 50% (weight).
27, according to the method for claim 16, wherein said ruthenium catalyst contains the metal Ru that is obtained by the reduction ruthenium compound.
28, according to the method for claim 27, wherein said ruthenium catalyst is the urging agent and contain and have average crystallite chi size and be not more than 200 metal Ru of carrier band not.
29, according to the method for claim 28, wherein ruthenium compound contains zn cpds, and based on the weight of ruthenium, the content of zinc is 0.1 to 50% (weight).
CNB981241395A 1997-04-16 1998-09-30 Process for producing cycloolefine Expired - Lifetime CN1159269C (en)

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JP04956498A JP4025411B2 (en) 1997-04-16 1998-03-02 Method for producing cycloolefin
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7947859B2 (en) 2005-08-26 2011-05-24 Asahi Kasei Chemicals Corporation Process for production of cycloolefin
CN114618487A (en) * 2022-05-12 2022-06-14 北京润景未来新材料科技有限公司 Bimetal alloy microcrystal catalyst for hydrogenation preparation of cyclohexene

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Publication number Priority date Publication date Assignee Title
CN104525192B (en) * 2014-12-22 2017-01-18 浙江大学 Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene

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Publication number Priority date Publication date Assignee Title
CA1267914A (en) * 1985-10-03 1990-04-17 Hajime Nagahara Process for producing cycloolefins

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7947859B2 (en) 2005-08-26 2011-05-24 Asahi Kasei Chemicals Corporation Process for production of cycloolefin
CN101198570B (en) * 2005-08-26 2011-11-02 旭化成化学株式会社 Process for production of cycloolefin
CN114618487A (en) * 2022-05-12 2022-06-14 北京润景未来新材料科技有限公司 Bimetal alloy microcrystal catalyst for hydrogenation preparation of cyclohexene
CN114618487B (en) * 2022-05-12 2023-01-31 北京润景未来新材料科技有限公司 Bimetal alloy microcrystal catalyst for hydrogenation preparation of cyclohexene

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CN1159269C (en) 2004-07-28

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