CN1381435A - Catalyst for liquid-phase dehydogenation of cyclohexanol - Google Patents
Catalyst for liquid-phase dehydogenation of cyclohexanol Download PDFInfo
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- CN1381435A CN1381435A CN 01112658 CN01112658A CN1381435A CN 1381435 A CN1381435 A CN 1381435A CN 01112658 CN01112658 CN 01112658 CN 01112658 A CN01112658 A CN 01112658A CN 1381435 A CN1381435 A CN 1381435A
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- hexalin
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Abstract
A catalyst for liquid-phase dehydrogenation of cyclohexanol contains Cu or its oxide, Pd and/or Pt or their oxide, and a metal chosen from Zn, Mg, Ca, Sr, Ni, Si, Al, Cr, Mn, Ni, Zr and Ti or its oxide. Its advantages are high activity, high conversion rate of cyclohexanol and high output rate of cyclohexanone.
Description
The present invention relates to be used for the catalyzer of cyclohexanol dehydrogenation, particularly dehydrogenation under liquid-phase condition prepares the catalyzer of pimelinketone about hexalin.
The pimelinketone most important applications is the raw material hexanolactam of preparation nylon-6, the raw material hexanodioic acid of nylon-66, and most pimelinketone is used for these two kinds and synthesizes.By-product hexalin when cyclohexane oxidation generates pimelinketone.Preparing cyclohexanol by cyclohexene hydration reaction is a technology newly developed.It is the integral part of mainly producing the adipic acid route that hexalin is produced pimelinketone by catalytic dehydrogenation, also is one of important method of producing pimelinketone.Hexalin gas-phase dehydrogenation synthesizing cyclohexanone is restricted by the gas chemistry equilibrated on thermodynamics, is the reversible thermo-negative reaction.If cyclohexanol dehydrogenation will obtain high per pass conversion, must under 380～450 ℃ high temperature, carry out without the catalyzer direct dehydrogenation.In order to improve speed of response and pimelinketone selectivity and to keep rational hexalin per pass conversion, generally all use dehydrogenation catalyst.The catalyst system of studying has many reports, industrial application mainly contain zinc calcium, copper magnesium, copper zinc and copper silicon System Catalyst.
At present, although catalyst system, model have nothing in common with each other, the industrialized technology of hexalin catalytic dehydrogenation is vapor phase process, and the catalyzer that is adopted is hexalin gas-phase dehydrogenation catalyzer.Except that Cu, the compound of Zn, Fe, Co, Ni, Cr, Sn etc. all can be used as the active ingredient of cyclohexanol dehydrogenation catalyst, but comprehensive many-sided factor, finally can realize industrial application catalyzer element seldom.The physical strength of Fe series catalysts and anti-caking power are higher, but selectivity is too low; The price of Co than the copper height but selectivity of product not as good as copper; The selectivity of Sn is also low.370～420 ℃ of zinc calcium catalyst service temperatures, the equilibrium conversion height, but because the temperature of reaction height, the pimelinketone selectivity is relatively poor.To improve selectivity is target, and having developed with copper is main low temperature modification catalyzer.Cu-series catalyst is with up to 99% pimelinketone selectivity, lower temperature of reaction and offseted the energy that the circulation unreacted reactant is consumed, and obtained application industrial.220～300 ℃ of copper magnesium catalyst service temperatures, but transformation efficiency obviously descends.The copper Si catalyst that Brazilian patent BR 89 03471 has reported cupric 85% was in normal pressure, 250 ℃, air speed 2.3 hours
-1, contain ketone 3.55% in the reaction raw materials, contained under the condition of alcohol 84.53%, cyclohexyl ring hexanone 0.1% and other impurity fixed bed reaction 22 days, per pass conversion is 55.6%, selectivity is 100%.Copper magnesium catalyst under the same terms, selectivity is identical, and per pass conversion only is 43.1%.Chinese patent CN 1056067A " multi component cyclohexanol dehydrogenation catalyst " has introduced a kind of CuO of containing, ZnO, MgO, CaO and micro-Na
2The catalyzer of O is electrolysis hydrogen, volume space velocity 1000 hours at 250～300 ℃ of activation temperatures, activated media
-1, soak time 6～12 hours, activation pressure 0.5～0.7MPa activation down, temperature of reaction is in the time of 250 ℃, the transformation efficiency guarantee value is more than 65%, selectivity 99.5～100%; Temperature of reaction was at 275～310 o'clock, and the transformation efficiency guarantee value is more than 75%, and selectivity is more than 99%.Therefore, mainly be Cu-series catalyst at the industrial dehydrogenation catalyst of obtaining application at present.Because the sintering temperature of copper is 280 ℃, the Cu-series catalyst service temperature is reduced to 200～300 ℃.Although have pimelinketone selectivity up to 99%, but being subjected to the gas chemistry balancing control, the hexalin per pass conversion obviously descends, generally be lower than 65%, cause the internal circulating load of unreacted hexalin in product purification and dehydrogenation reactor system to increase, cause energy consumption, material consumption to increase, the pimelinketone yield descends.For this reason, people take various measures to improve the hexalin per pass conversion.On technology, adopt among the Chinese patent CN 1056067A " multi component cyclohexanol dehydrogenation catalyst " and improve the temperature of reaction method, but this catalyzer is affected work-ing life.Chinese patent CN1207383A " improvement of cyclohexanol dehydrogenation method " adopts and adds the not water vapour of chloride ion-containing continuously in dehydrogenation reactor, but dividing potential drop reduction effect is limited.U.S. Pat P4918239 " hexalin oxydehydrogenation prepares the method for pimelinketone " adds certain density gaseous oxidizing agent in the hexalin charging by other, 180～280 ℃ of oxydehydrogenations improve transformation efficiency on the CuO-ZnO catalyzer, yet, compare its selectivity with method of dehydrogenating and descend to some extent.
The objective of the invention is to exist activity of such catalysts lower in order to overcome in the above-mentioned document, the hexalin transformation efficiency is low, the shortcoming that the pimelinketone yield is low, a kind of new catalyzer that is used for the hexalin dehydrogenation in liquid phase is provided, this catalyzer has hexalin transformation efficiency height in the reaction of hexalin dehydrogenation in liquid phase, the high characteristics of pimelinketone yield simultaneously.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer that is used for the hexalin dehydrogenation in liquid phase comprises following component by weight percentage:
A) metal of copper or oxide compound 20～74%;
B) palladium is or/and the metal of platinum or oxide compound 0.001～2.0%;
C) at least a metal or the oxide compound 24～78% that is selected from zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium.
In the technique scheme, the metal of copper or oxide compound consumption preferable range are 34～54% by weight percentage, palladium is or/and the metal of platinum or oxide compound consumption preferable range are 0.01～1.0%, and at least a metal or the oxide compound consumption preferable range that is selected from zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium is 43～63%.Metal or the preferred version in the oxide compound at zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium are at least a metal or the oxide compound that is selected from magnesium, calcium, strontium or barium, its consumption is 0.1～5% by weight percentage, and the preferable range of consumption is 0.5～2%.By weight percentage, also contain at least a metal or the oxide compound that is selected from sodium, potassium or caesium in the catalyzer, its consumption is 0.01～2.0%, and preferable range is 0.05～1.0%.The component of copper can metallic forms add in the composition of catalyzer, or the adding of the form of the reduction precursor metal oxide of metal and metal, and wherein the add-on of metal oxide is 0～0.7% by weight percentage.
Hexalin dehydrogenation in liquid phase catalyzer of the present invention, can make catalyst precursor by oxide catalyst preparation method commonly used, activate and make catalyzer by containing gas phase mixture such as reducing gas such as hydrogen again such as hybrid system, pickling process, the precipitator method.For example, carry out even coprecipitation reaction, filtration, drying, roasting by metallic salt and precipitation agent and make catalyst precursor, the gas phase mixture by hydrogen and nitrogen makes catalyzer in 250～300 ℃ of activation temperatures, high-speed, soak time activation in 6～36 hours again.Be prepared as follows:
1, needs 1 liter of copper nitrate aqueous solution of proportioning preparation in accordance with regulations with deionized water dissolving 250 grams, prepare 1 liter of magnesium nitrate, nitrocalcite, strontium nitrate, nitrate of baryta, aqueous solution of aluminum nitrate;
2, the aqueous solution that needs 1 liter of soluble zinc salt of proportioning preparation with deionized water dissolving 180～300 gram in accordance with regulations, such as nitrate, perhaps acetate, perhaps formate, the perhaps aqueous solution of oxalate;
3, the aqueous solution that needs proportioning preparation 1 liter of silicon, chromium, manganese, nickel, zirconium or titanium salt with deionized water dissolving 150～300 grams in accordance with regulations;
4, the aqueous solution that needs 1 liter of sodium hydroxide of proportioning preparation with deionized water dissolving 200 grams in accordance with regulations;
5, with the above-mentioned copper nitrate aqueous solution that is mixed with, magnesium nitrate, nitrocalcite, strontium nitrate, nitrate of baryta, aqueous solution of aluminum nitrate, zinc salt solution, the aqueous solution of silicon, chromium, manganese, nickel, zirconium or titanium salt, mix by 200～800: 1～400: 100～600: 0～400 volume ratio, make mixed solution A;
6,40～95 ℃ of temperature, pH value 7.2～13 constantly under the stirring condition, with above aqueous sodium hydroxide solution that is mixed with and mixed solution A, and flows the adding precipitation reactor, precipitates 0.5～5.0 hour.
7, then 50～95 ℃ of temperature, pH value 7.5～12 under the stirring condition, wore out 0.5～5 hour, made the oxyhydroxide mixed crystal throw out of copper, zinc, magnesium, calcium, strontium, barium, aluminium, silicon, chromium, manganese, nickel, zirconium or titanium.
8, with filter method the mixed crystal mixture is separated from solution, and repeatedly washing.
9, need the aqueous solution of proportioning preparation with the palladium salt or the platinum salt brine solution of the solubility that needs the proportioning preparation in accordance with regulations, the oxyhydroxide that is selected from sodium, potassium or caesium in accordance with regulations, flood the mixed crystal throw out respectively.
10, at 100～135 ℃ of oven dry mixed crystal throw outs, add the mixing of 1～5% graphite again and mill, by 80 mesh sieves.
11,, after the suction part moisture regain, make catalyst prod by common forming method 320～600 ℃ of roastings 1～8 hour.
12, catalyst prod through hydrogen at 180～300 ℃, pressure 0.5～1.5MPa, WHSV150～1500 hour
-1Reduce under the condition, obtain being used for the catalyzer of hexalin dehydrogenation in liquid phase
It is to guarantee that reaction system is a liquid phase that this hexalin dehydrogenation in liquid phase catalyzer is used for the suitable reaction condition that the hexalin dehydrogenation in liquid phase prepares pimelinketone.When cyclohexanol dehydrogenation temperature of reaction general range is 150～400 ℃, optimum range is 190～250 ℃; The reaction pressure general range is normal pressure～3.5MPa, when optimum range is 0.5～1.2MPa, and hexalin per pass conversion 70～100%, pimelinketone selectivity 85～96%.The raw material hexalin needn't gasify and bring reactor into by carrier gas, and directly the liquid phase sample introduction carries out the liquid-phase catalysis dehydrogenation reaction, and energy consumption reduces.Since the pimelinketone of hydrogen that this catalyzer dehydrogenation under the suitable reaction conditions generates and one of reaction raw materials hexalin, reaction product gas-liquid mutually in the composition distribution differ greatly, the hydrogen major part that dehydrogenation generates breaks away from liquid-phase reaction system immediately, make the cyclohexanol dehydrogenation reaction not restricted by the liquid phase chemical equilibrated, to obtain the hexalin dehydrogenation in liquid phase transformation efficiency 70～100% more much higher than hexalin gas-phase dehydrogenation transformation efficiency, significantly reduce even do not have the circulation between reactive moieties, product purification part of unreacted hexalin, energy consumption reduces.Liquid product can be carried the high-boiling-point impurity that adheres to catalyst surface such as oligopolymer, ester class, X wet goods material to leave reactive moieties secretly under suitable reaction conditions, and constantly the cleaning catalyst surface suppresses further coking.But this catalyzer raw materials used various operational path synthetic hexalin, especially lower-boiling impurities mainly are the low hexalin of cyclohexanone content less.
In the dehydrogenation catalyst of the present invention,, make catalyzer have advantages of high catalytic activity and selectivity owing to select for use the metal of copper or oxide compound as Primary Catalysts.Select at least a metal or the oxide compound that is selected from zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium for use, improved the catalytic performance of catalyzer, make catalyzer have higher selectivity, the stability in use that has improved catalyzer simultaneously is with active.Select palladium for use in the catalyzer or/and the metal of platinum or oxide compound make catalyzer have the ability that adapts to the liquid-phase catalysis dehydrogenation, further improved activity of such catalysts simultaneously, reduced the temperature of reaction.In the liquid-phase catalysis certain embodiments, because the hydrogen of one of product constantly is discharged from the reaction solution system, molecular balance is constantly broken, thereby improved feed stock conversion, improved the yield of product pimelinketone, make the hexalin transformation efficiency reach as high as 100%, product pimelinketone yield reaches as high as 81%, has obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
1, with deionized water dissolving 250 gram Cu (NO
3)
2, prepare 1 liter of copper nitrate aqueous solution;
2, with deionized water dissolving 250 gram Mg (NO
3)
2, prepare 1 liter of magnesium nitrate aqueous solution;
3, with deionized water dissolving 200 gram Zn (NO
3)
2, prepare 1 liter of zinc nitrate aqueous solution;
4, with deionized water dissolving 290 gram Ni (NO
3)
3, prepare 1 liter of nickel nitrate aqueous solution;
5, with deionized water dissolving 200 gram NaOH, prepare 1 liter of aqueous sodium hydroxide solution;
6, with the above-mentioned cupric nitrate that is mixed with, magnesium nitrate, zinc nitrate, nickel nitrate aqueous solution, by 550: 36.9: 300: 4.25 volume ratio is mixed, and makes mixed solution A;
7,60 ℃ of temperature, pH value 8.5 constantly under the stirring condition, with above aqueous sodium hydroxide solution that is mixed with and mixed solution A, and flows the adding precipitation reactor, precipitates 2 hours.
8, then 65 ℃ of temperature, pH value 7.8 under the stirring condition, wore out 1 hour, made the oxyhydroxide mixed crystal throw out of copper, zinc, magnesium, nickel.
9, with filter method the mixed crystal mixture is separated from solution, and repeatedly washing.
10, with palladium chloride aqueous solution, the 0.05N cesium hydroxide aqueous solution of 0.05N, flood the mixed crystal throw out respectively.
11, at 120 ℃ of oven dry mixed crystal throw outs, add the mixing of 4% graphite again and mill, by 80 mesh sieves.
12,, after the suction part moisture regain, make catalyst prod by common forming method 400 ℃ of roastings 3 hours.
13, catalyst prod through hydrogen at 250 ℃, pressure 1.0MPa, WHSV300 hour
-1Reduce under the condition, obtain being used for the catalyzer of hexalin dehydrogenation in liquid phase.The weight percentage of catalyzer each component is listed in table 1.[embodiment 2～6]
Each Step By Condition according to embodiment 1 prepares catalyzer, just changes the kind and the weight percentage of catalyst component, and the catalyzer that makes composition is listed in table 1.
Table 1 catalyst component table
[embodiment 7]
| Embodiment 1 | Embodiment 2 |
| ????Cu?70％ | ????Cu?50％ |
| ????ZnO?26.18％ | ????ZnO?34％ |
| ????MgO?1.8％ | ????CaO?9.998％ |
| ????Pd?1.5％ | ????Pd?0.002％ |
| ????Si?0.5％ | ????Al?5.9％、Mn?0.05％ |
| ????Cs?0.02％ | ????K?0.05％ |
| Embodiment 3 | Embodiment 4 |
| ????Cu?10％、CuO?59％ | ????Cu?40％ |
| ????ZnO?25％ | ????ZnO?40％ |
| ????BaO?5％ | ????MgO?12％、CaO?0.8％ |
| ????Pt?0.1％ | ????Pd?0.3％ |
| ????Ni?0.8％、Cr?0.1％ | ????Zr?3.0％、Si?3.0％ |
| ????---- | ????Na?0.1％、K?0.8％ |
| Embodiment 5 | Embodiment 6 |
| ????Cu?40％ | ????Cu?22％ |
| ????Zn?48.45％ | ????ZnO?44.68％ |
| ????MgO?8％、CaO?1.8％ | ????MgO?20％、SrO?1.0％ |
| ????Pd?0.05％ | ????Pd?0.02％ |
| ????Ti?0.2％、Si?0.8％ | ????Ni?6.3％、Zr?5.0％ |
| ????Na?0.1％、K?0.6％ | ????Na?0.1％、K?0.9％ |
The cyclohexanol dehydrogenation catalyst that embodiment 1～6 makes is checked and rated under different reaction conditionss, and reaction conditions is listed in table 2, and reaction result is listed in the table 3.
Table 2
| Embodiment | Hexalin content % | The loaded catalyst milliliter | Temperature of reaction ℃ | Reaction pressure MPa |
| Embodiment 1 | ????94 | ????20 | ????150 | ????0.1 |
| Embodiment 2 | ????94 | ????20 | ????190 | ????0.5 |
| Embodiment 3 | ????99 | ????20 | ????210 | ????0.6 |
| Embodiment 4 | ????99 | ????20 | ????225 | ????1.0 |
| Embodiment 5 | ????99 | ????20 | ????240 | ????1.2 |
| Embodiment 6 | ????99 | ????20 | ????300 | ????3.5 |
Table 3
| Embodiment | The hexalin per pass conversion, % | The pimelinketone selectivity, % |
| Embodiment 1 | ????70 | ????90 |
| Embodiment 2 | ????78 | ????97 |
| Embodiment 3 | ????85 | ????92 |
| Embodiment 4 | ????90 | ????90 |
| Embodiment 5 | ????95 | ????85 |
| Embodiment 6 | ????100 | ????70 |
Claims (8)
1, a kind of catalyzer that is used for the hexalin dehydrogenation in liquid phase comprises following component by weight percentage:
A) metal of copper or oxide compound 20～74%;
B) palladium is or/and the metal of platinum or oxide compound 0.001～2.0%;
C) at least a metal or the oxidation that is selected from zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium
Thing 24～78%.
2,, it is characterized in that the metal or the oxide compound consumption of copper are 34～54% by weight percentage according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 1.
3,, it is characterized in that palladium is or/and the metal of platinum or oxide compound consumption are 0.01～1.0% by weight percentage according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 1.
4,, it is characterized in that at least a by weight percentage metal or the oxide compound consumption that is selected from zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium is 43～63% according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 1.
5, according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 1, it is characterized in that at least a metal or the oxide compound that is selected from magnesium, calcium, strontium or barium in the metal of zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium or the oxide compound, its consumption is 0.1～5% by weight percentage.
6, according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 5, it is characterized in that at least a metal or the oxide compound that is selected from magnesium, calcium, strontium or barium in the metal of zinc, magnesium, calcium, strontium, barium, silicon, aluminium, chromium, manganese, nickel, zirconium or titanium or the oxide compound, its consumption is 0.5～2% by weight percentage.
7, according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 1, it is characterized in that also containing at least a metal or the oxide compound that is selected from sodium, potassium or caesium in the catalyzer by weight percentage, its consumption is 0.01～2.0%.
8, according to the described catalyzer that is used for the hexalin dehydrogenation in liquid phase of claim 7, it is characterized in that also containing at least a metal or the oxide compound that is selected from sodium, potassium or caesium in the catalyzer by weight percentage, its consumption is 0.05～1.0%.
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|---|---|---|---|
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| CN1150990C CN1150990C (en) | 2004-05-26 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247854A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing cyclohexanone by virtue of cyclohexanol dehydrogenation as well as preparation method thereof |
| CN102247866A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst used for preparation of cyclohexanone by dehydrogenation of cyclohexanol and preparation method thereof |
| CN102247855A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof |
| CN101428228B (en) * | 2008-09-11 | 2012-03-07 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and method of producing the same |
| CN108892607A (en) * | 2018-08-14 | 2018-11-27 | 山东新和成药业有限公司 | A kind of preparation method of laurine |
| CN109836321A (en) * | 2017-11-29 | 2019-06-04 | 国际香料和香精公司 | The method for preparing A Fuman ketone fragrance |
| CN112138676A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Catalyst for preparing o-phenylphenol and preparation method thereof |
-
2001
- 2001-04-18 CN CNB011126582A patent/CN1150990C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428228B (en) * | 2008-09-11 | 2012-03-07 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and method of producing the same |
| CN102247854A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing cyclohexanone by virtue of cyclohexanol dehydrogenation as well as preparation method thereof |
| CN102247866A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst used for preparation of cyclohexanone by dehydrogenation of cyclohexanol and preparation method thereof |
| CN102247855A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof |
| CN102247855B (en) * | 2011-07-26 | 2013-03-13 | 烟台大学 | Catalyst for preparing methyl ethyl ketone by virtue of sec-butyl alcohol dehydrogenation and preparation method thereof |
| CN102247854B (en) * | 2011-07-26 | 2013-06-19 | 烟台大学 | Catalyst for preparing cyclohexanone by virtue of cyclohexanol dehydrogenation as well as preparation method thereof |
| CN109836321A (en) * | 2017-11-29 | 2019-06-04 | 国际香料和香精公司 | The method for preparing A Fuman ketone fragrance |
| CN108892607A (en) * | 2018-08-14 | 2018-11-27 | 山东新和成药业有限公司 | A kind of preparation method of laurine |
| CN112138676A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Catalyst for preparing o-phenylphenol and preparation method thereof |
| CN112138676B (en) * | 2019-06-26 | 2023-06-20 | 中国石油化工股份有限公司 | Catalyst for preparing o-phenylphenol and preparation method thereof |
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