CN107930640A - The catalyst of 4 methyl of one-step method coproduction, 2 pentanone and 4 methyl, 2 amylalcohol - Google Patents
The catalyst of 4 methyl of one-step method coproduction, 2 pentanone and 4 methyl, 2 amylalcohol Download PDFInfo
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- CN107930640A CN107930640A CN201610892292.3A CN201610892292A CN107930640A CN 107930640 A CN107930640 A CN 107930640A CN 201610892292 A CN201610892292 A CN 201610892292A CN 107930640 A CN107930640 A CN 107930640A
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
Catalyst disclosed by the invention belongs to the technical field of the application and development of acetone downstream product, disclosure is using copper, alkaline-earth metal, cerium and chromium as load component, aluminium oxide of the selection with abundant acid-base property, silica or alumina silica complex carrier promote reaction, used under relatively mild reaction condition, the yield of 4 methyl, 2 pentanone is higher than the palladium-resin catalyst that existing commercial plant uses, while 4 methyl of by-product economy, 2 amylalcohol.Catalyst shows preferable stability.Catalyst cost is substantially less than existing palladium catalyst, has preferable economic benefit.
Description
Technical field
The present invention relates to a kind of catalyst of ketone condensation, more specifically to being raw material through one-step method coproduction using acetone
The catalyst of 4-methyl-2 pentanone and 4- methyl -2- amylalcohols.
Background technology
4-methyl-2 pentanone, is commonly called as methyl iso-butyl ketone (MIBK) (English abbreviation MIBK), is in a kind of important solvent and chemical industry
Mesosome, receives much concern because of its excellent performance, has aromatic ketone smell, water white transparency, boiling point belongs to medium boiling point, and dissolving power is non-
Chang Qiang, can may be used as coating, ethyl cellulose, nitrocellulose, recording record with numerous immiscible organic solvents such as alcohol, benzene, ether
Image-tape, paraffin, a variety of natural or synthetic resin solvents, dewaxing agent, rare earth metal extractant, initiators for polymerization, surface are lived
Property agent, medicine, the raw material of pesticide extractant and rubber antioxidant, be Speciality Petrochemicals intermediate more well sold and in short supply at present,
Many application fields have irreplaceability, the still annual a large amount of imports in present China.
Existing market is seen, 4-methyl-2 pentanone mainly uses acetone as raw material and produced.According to reaction process point
For three-step approach and one-step method.Because one-step method has the advantages that short technological process, small investment, feed stock conversion are high, have become master
The synthesis route wanted.
The reaction that the process of acetone three-step approach production methyl iso-butyl ketone (MIBK) illustrates acetone synthesis 4-methyl-2 pentanone is gone through
Journey：Condensation, acid-catalyzed dehydration and selection hydrogenation.With the continuous development and progress of catalysis technique, people begin one's study by this three
The multifunction catalyst that kind course is integrated in one.German Veba-Chemie companies take the lead in building One-step production dress in nineteen sixty-eight
Put, its acetone conversion per pass is that 34.4%, MIBK selectivity is 96.5%.German two company of Veba and Taxaco selects strong
Acid cation exchange resin and the Pd for having hydrogenating function to olefinic double bonds make catalyst, prepare relatively difficult.The U.S. in recent years
Mobil companies develop Pd-NSM-5 modified zeolite catalysts, it is only necessary to impregnate, roast and can prepare.In recent years, China
Multifunction catalyst, such as Pd/ resin catalysts, the molecular sieve catalyst of industrial application are begun one's study and develop, using no amine
Method synthesis ZSM-5 molecular sieve is carrier, using metal Pd as active component, using metallic copper as cocatalyst component, synthesis 4- methyl-
2 pentanone.Liu Zili etc. prepares BaO/ aluminium oxide catalysts using infusion process.Li Hongxia is using HZSM-5 molecular sieves as carrier, load
More metal active constituents such as Pd, Cu, Zn, Ni, in 160 DEG C of reaction temperature, reaction pressure 18Kg/cm2Liquid-phase reaction condition under,
The conversion ratio of acetone be the high selectivity of 42.7%, MIBK up to 95.6%, but do not industrialize.Shen Yanming etc. uses precipitation side
Method prepares Cu-MgO-Al2O3Catalyst, acetone conversion 71.7%, MIBK are selectively 51%, and document is not provided and urged
The agent service life.
4- methyl -2- amylalcohols, are commonly called as methyl isobutyl carbinol (English abbreviation MIBC), are excellent medium-boiling solvents, main
To be used as the solvent of dyestuff, oil, rubber, resin, paraffin, NC Nitroncellulose and ethyl cellulose etc., as nitrocellulose
The atent solvent of paint, can increase the gloss and planarization of coating, improve general red performance, be used as in lube oil additive manufacture molten
Agent etc..For the raw material of organic synthesis, mineral floating lotion, such as extracts silicon and sulfuric acid copper mine, it may also be used for brake-fluid.In recent years
Come, the demand of 4- methyl -2- amylalcohols continues to increase, and market prospects are very optimistic, and price also remains high.
Continuous with domestic MIBK devices is built, and the simple device for producing MIBK does not have profitability, mostly
Device is in halt production or underrun state.Insider begins look for the downstream product of MIBK to improve the profit water of device
The gentle ability to ward off risks, one of them important product is exactly MIBC, its price also costly, has preferable market price
Value.Based on this market demand, inventor develops the catalyst of the present invention.
Document and report are made a general survey of, the industrialized catalyst in the field is still Pd/ resin catalysts at present, the longevity of catalyst
Life is 9-12 months, and the catalyst cannot produce or by-product 4- methyl -2- amylalcohols (MIBC).Other catalyst are there is not yet work
Industryization is reported.Inventor passes through thoroughgoing and painstaking research, and the vital factor for finding to restrict catalyst stability is acetone
The condensation product produced is condensed, the MIBK of generation can further occur condensation reaction, produce the condensation product of bigger.These condensation products cover
Cover in catalyst surface, cause catalytic active site covering inactivation.
The content of the invention
The palladium catalyst service life of industrial application is shorter in the prior art, costly, and your widely studied non-gold
Metal catalyst still cannot meet industrial requirement, and inventor has carried out deeply and carefully non-metallic catalyst according to enterprise requirements
Research, by the experimental study of several years, obtain ideal catalyst and technology.
The concrete technical scheme of the present invention is as follows：
The present invention provides a kind of one-step method coproduction 4-methyl-2 pentanone and the catalyst of 4- methyl -2- amylalcohols, its feature
It is, the catalyst includes carrier and load component copper, alkaline-earth metal, cerium and chromium, wherein alkaline-earth metal in the form of an oxide
In the presence of.
Inventor passes through a large number of experiments, performance more preferably catalyst has been filtered out, with the mass percent of the catalyst
For 100% meter, the catalyst includes consisting of：
(1) copper, for copper in terms of metallic state, mass percentage content is 5%~15%；
(2) alkaline-earth metal, converts and is calculated for metallic state, and mass percentage content is 0.05%~2%；
(3) cerium, for cerium in terms of metallic state, mass percentage content is 0.1%~4%；
(4) chromium, converts and is calculated for metallic state, and mass percentage content is 2%~15%；
(5) carrier, the surplus in addition to the content of metallic state and the load component of metal oxidation state.
Catalyst prepared by the present invention needs to carry out reduction treatment before use, is metal by most copper reductions
State, but some components such as alkaline-earth metal cannot be reduced to metallic state, for the ease of the content of statement load component, load group
Divide to use and calculated by converting for metallic state on the basis of constituent content.
Alkaline-earth metal in the copper-based catalysts can be combination more than one or both of magnesium, calcium and barium, from
From the point of view of catalyst synthesizing methyl isobutyl ketone, one or both of magnesium and calcium are more preferably.
In order to better disperse load component, catalyst of the invention used carrier, such as the carrier for aluminium oxide,
Silica, aluminium oxide-silicon oxide complex carrier or molecular sieve.From the point of view of the condensation, dehydration and hydrogenation process that acetone is undergone, institute
The aluminium oxide that aluminium oxide is more preferably the modified aluminium oxide of acid or alkali modification is stated, sour modification or alkali modification can promote to be condensed and take off
Water process.The silica can also select the silica using the modified silica of acid or alkali modification.Stablize from carrier structure
Property angle see, be more favorable, the more preferably modified aluminium oxide-oxygen of acid certainly using aluminium oxide-silicon oxide complex carrier
The aluminium oxide-silicon oxide complex carrier of SiClx complex carrier or alkali modification.So-called acid modification can be used when carrier is molded
Phosphoric acid, sulfuric acid, hydrofluoric acid or boric acid are modified.So-called alkali modification can add alkaline metal salt for example when carrier is molded
Lanthanum nitrate, alkali metal salt, alkali salt etc. carry out alkali modification.
In catalyst the source of copper metal may be selected from water miscible metal salt for example nitrate, sulfate, villaumite, acetate,
Oxalates and bromide, or selected from metallic copper, such as copper metal plate.More specifically water-soluble metal salt is selected from copper nitrate, chlorination
One kind in one or more in copper, cupric oxalate, copper sulphate, copper acetate, more preferably copper nitrate, copper acetate and cupric oxalate
It is or a variety of.
Cerium is that another important constituent component, suitable cerium add and drastically increase catalyst in catalyst of the present invention
Activity and selectivity.After auxiliary agent cerium adds, catalyst activity and selectivity etc. represents the index of catalyst reaction performance significantly
Improve, reason for that is probably many：Cerium improves the electronics form of copper.Cerium plays electricity to the copper catalyst after reduction
Minor structure promotor action, copper is mainly zeroth order after reduction, and cerium is reduced to 3+ valencys from 4+ valencys, plays interaction therebetween,
Electronics is inclined to cerium by copper, causes the electronics degree of unsaturation of copper to increase, so as to influence the electronic variable of the carbonyl of acetone, promotes reaction
Carry out.
It is more unexpected, the inventors discovered that, by impregnating, spraying, being co-precipitated, deposition-precipitation, ammonia still process precipitation, colloidal sol-
Gel, dissolve the copper-based catalysts prepared for suction filtration after alloy and ball grinding method, and auxiliary agent cerium improves the effect of catalyst reaction performance
Fruit is more obvious.
The source of cerium is not limited, can be known all cerium-containing compounds.The source of the cerium further optimized has
Ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate, cerium chloride, cerous nitrate, cerous carbonate, cerium fluoride, cerous acetate, cerium oxalate etc..
One or more of the alkaline-earth metal in calcium, magnesium, barium in the catalyst of the present invention.Alkaline-earth metal source can be with
For water miscible nitrate, carbonate, villaumite, phosphate, sulfate, acetate, fluoride, hydroxide etc..It is more specific and
Speech, such as one or more of its source in calcium nitrate, calcium dihydrogen phosphate, magnesium nitrate, magnesium phosphate, barium nitrate.
The feed postition of alkali earth metal can be selected from any one in the following manner：Dipping, mediate, precipitation,
Added after being dissolved in deposition-precipitation or sol-gel process together with mantoquita；Blending, ball milling, melting the methods of in copper
Salt adds together or substep adds；Dipping, precipitation, deposition-precipitation either in sol-gel process with mantoquita respectively or
Substep adds；Added in catalyst precursor, filter cake after the drying obtained in such as precipitation, deposition-precipitation or sol-gel
Or in xerogel, or in material after Roasting Decomposition；Either playing the addition of the formative stages such as piece or extrusion.
The source of chromium may be selected from water miscible metal salt such as chromic nitrate, chromium sulfate, chromate, chromium chloride, again in catalyst
Chromate etc..More specifically water-soluble metal salt is a kind of or more in chromic nitrate, ammonium dichromate, chromium sulfate and chromium chloride
Kind.
As previously described, catalyst of the invention is not done here also containing the oxide for being typically considered to carrier function
Special limitation, selected from silica, aluminium oxide, silica-alumina compound, diatomite, calcium silicates, zirconium oxide, titanium oxide
One or more.In fact, these carriers are not only to play a supporting role, additionally it is possible to assist divided active component and rush
Into condensation of acetone and dehydration, it is strong that these carriers affects structural behaviour, product and the raw material of catalyst spreading wherein, machinery
The critical index such as degree, activity and stability.
Alumina catalyst support can be selected from the hydrogen-oxygen of the productions such as nitrate method, sulfuric acid process, carbonatation process, Bayer process, rapid dehydration method
Change the standby aluminium oxide of aluminum.Because alumina ratio is more common, not reinflated narration here.
Support Silica can be selected from waterglass precipitate method, SiO 2 powder, teos hydrolysis, Ludox etc..
The SiO 2 powder can be obtained by ball milling after drying after chemical deposition, waterglass precipitate or be that silicon is molten
The methods of glue is spray-dried obtains, its size is selected from 10nm~500 μm；The gross porosity microballoon dioxy produced such as Haiyang Chemical Plant, Qingdao
(average pore size 8.0-12.0nm, specific surface area are 300~600m to SiClx2/ g, pore volume are 0.8~1.1ml/g), and for example Guangzhou
The people chemical plant production precipitated silica (silica (SiO2) content % >=95.0, fineness (325 screen residue) %≤
1.8, specific surface area is 400~600m2/ g) or active carbon white, and for example goldschmidt chemical corporation aerosil AEROSIL
200, it is 200m than surface2/ g, the silicon dioxide microsphere that and for example self-control spray drying obtains, is 400~500m than surface2/ g,
Size is 2~30 μm.SiO 2 powder can add in precipitation or deposition-precipitation as carrier.The water glass
Glass direct precipitation method refers to using waterglass as raw material, and acidic precipitation agent or ion precipitation agent are added in waterglass, as sulfuric acid,
Hydrochloric acid, nitric acid, acetic acid, calcium nitrate, zirconyl nitrate, zirconium oxychloride, magnesium nitrate, cobalt nitrate etc..Precipitating reagent forms white after adding
Jelly, washing uses afterwards for several times or the precipitation method of progress other components add on basis herein.Ethyl orthosilicate be
Prepared by sol-gel process uses in the catalyst of the present invention.Ludox can be used directly into precipitation, sink as liquid silicon source
In the sediment system of the product-precipitation method.
In order to improve the heat endurance of aluminium oxide, mechanical strength, pore structure and surface nature, it is inorganization that some can be added
Compound is modified.Such as add silica in aluminium oxide and be modified.Such as add silicon in aluminium hydroxide hydrogel
Gel or silica-alumina gel, can significantly change the texture property of aluminium oxide and the acid-base property of carrier.Rare-earth oxidation can also be added
Thing significantly improves the heat endurance of aluminium oxide and changes the acid-base property of carrier.Can also add molecular sieve, barium monoxide, magnesia,
Boric acid, phosphoric acid and hydrofluoric acid carry out improvement carrier property.
Support Silica or aluminium oxide are also likely to be to be used as binding agent in the catalyst prepared as melting-suction method
Add so that the catalyst fines of gained can be shaped to the required shape of the present invention.
The shape of catalyst of the present invention can be diversified, such as spherical, strip, column, ring-type, size
Between 0.3~15mm, more preferably between 0.5~3mm, the requirement of this size is mainly fixation according to the present invention
Bed reactor design, with convenient installation, reduces the requirement such as bed layer pressure.These knowledge are that professional and technical personnel institute is ripe
Know.
Method for preparing catalyst of the present invention can be obtained by existing catalyst preparation technology, such as infusion process, from
Sub- exchange process, blending method, mediate method, co-precipitation, deposition-precipitation, steaming ammonium precipitation, melting-suction filtration, ball milling and sol-gel etc.
Method.Preferred method includes a kind of or more in dipping, co-precipitation, deposition-precipitation, sol-gel and ball grinding method
Kind, which combines, to be prepared, these prepare catalyst method and are well known to those skilled in the art mostly as existing mature technology, at this
There is detailed introduction in the books of field, such as Huang Zhong Tao is written《Industrial catalyst design and development》, Gerhard Ertl religions
Award etc. written《Preparation of Solid Catalysts》.
For example, soluble copper salt, alkali salt, cerium salt and chromic salts can be dissolved as aqueous solution, using dipping
Method is supported on carrier, can be impregnated several times according to carrier water absorption rate, or these types of salt is dissolved as aqueous solution point respectively
Step dipping, then dry and Roasting Decomposition, then reduced, the temperature and program decomposed and reduced, those skilled in the art
It can be carried out according to the temperature programmed reduction characterization result of prepared catalyst.
For another example soluble copper salt, alkali salt, cerium salt and chromic salts can be dissolved as aqueous solution, it is warming up to certain
Temperature, adds aqueous sodium carbonate under agitation, is 7~8 to pH value, then adds support powder, keeps the temperature aging certain time,
Filtering, washing, drying, granulation, Roasting Decomposition, shaping.
The catalyst of the present invention will be reduced before use, and reducing gas can be the mixing of hydrogen, hydrogen and nitrogen
Gas, hydrogen content can be any content in hydrogen nitrogen mixed gas, such as 2vol% to 80vol%, can also use higher amount
Gas.Consider from the temperature control angle of catalyst reduction, preferably the relatively low gaseous mixture of hydrogen content.During reduction, gas
Air speed is the bigger the better.Air speed is big, quickly can remove the heat for reacting generation in time, maintains reaction bed temperature relatively more flat
Surely, temperature runaway damage catalyst will not be produced.Such as the air speed of gaseous mixture is 300~5000m3/m3·h-1.The temperature of reduction can root
Determined according to the composition of specific catalyst, can be with 5~20 DEG C/h for the catalyst of the present invention, preferably 5~10 DEG C/h
Speed step up reaction bed temperature, 100 DEG C of annexes stop 2-8 it is small when, then with 5~20 DEG C/h, preferably 5
~10 DEG C/h of speed steps up reaction bed temperature, until 250~300 DEG C, keep 2-48 small at this temperature
When.Then room temperature is slowly dropped to, such as rate of temperature fall is 5~20 DEG C/h.It is cooled to room temperature, is switched to nitrogen, gradually to nitrogen
Gas is mixed into hydrogen, gradually steps up hydrogen usage to improve the hydrogen content in gaseous mixture.According to the change of catalyst temperature at any time
The dosage of hydrogen is adjusted, avoids reaction bed temperature too high, such as no more than 50 DEG C.If catalyst is gone back in the reactor
Original, temperature is down to reaction temperature and can feed intake use after catalyst reduction.
The catalyst of the present invention may be used as in fixed bed reactors, and reaction condition is：Reaction temperature for 100~190 DEG C,
Reaction pressure is 0.8~2.5MPa, acetone air speed is 0.1~1.5h-1, hydrogen and acetone the ratio of amount of material be 1~6:1.
Reaction temperature rise is conducive to improve acetone conversion, is conducive to acetone and condensation reaction and dehydration occurs.Increase reaction pressure
Power is more advantageous to increase hydrogenation reaction intensity, and isopropanol selectively increases.Acetone air speed influences less within the above range, air speed
Excessive, acetone conversion reduces, and once through yield reduces.Hydrogen influences less reaction, but be not easy in the case of enough
More, hydrogen influences residence time of the material in catalyst bed.
The catalyst of the present invention is compared with the palladium-resin catalyst used in existing industry, and catalyst is of low cost, and palladium is urged
Agent price per ton is up to hundreds of thousands member, or even member up to a million, and the catalyst of the present invention be its 1/10th.Preparation process
Relative ease, easily manipulates, and palladium catalyst polymerization will prepare granular resin first, and then palladium load is got on by exchanging, and
And the organic matter on resin is easily lost in, pollution reactor product and increase product colourity, and the catalyst of the present invention will not be lost in.
The technological operation window narrows of palladium-resin catalyst, temperature is excessive to be easy to cause catalyst inactivation, and acid amount reduces, and the present invention
Catalyst has wider temperature operating window.The structural stability and operational suitability of catalyst determine the catalysis of the present invention
Agent has higher stability and service life.Palladium catalyst only produces a kind of product i.e. methyl iso-butyl ketone (MIBK), and the catalysis of the present invention
Agent can not only produce methyl iso-butyl ketone (MIBK), can also produce 4- methyl -2- amylalcohols, adaptation energy of the industrial installation to market
Power is stronger, anti-loss ability increase.
Embodiment
The catalyst of the present invention is explained further by way of examples below, but the present invention is not limited to this.
Embodiment 1
58.2 grams of copper nitrates, 57 grams of magnesium nitrates and 36.3 grams of cerous nitrates are dissolved in 350 grams of water in beaker, water is made
Solution I.29 grammes per square metre ammonium chromates are dissolved in 68 grams of water in another beaker, aqueous solution II is made.In stirring and solution temperature
At 70 DEG C of degree, ammonium dichromate aqueous solution II is poured into the beaker of aqueous solution I, be then titrated to 30wt% aqueous sodium carbonates
The pH value of reaction solution is 7.0.Then 357 grams of boehmite powders are added.Boehmite is by three doses of the Jiangsu limited public affairs of industry
Department's production, specific surface area 290m2/ g, pore volume 0.9mL/g.
Then when aging 4 is small at 75 DEG C, then filters and wash, until sodium ions content is less than 0.05%.
It is dry, it is granulated, then the Roasting Decomposition at 350 DEG C.Finally beat piece is into graininess, particle diameter
Then according to temperature-programmed mode 5vol% hydrogen and the gaseous mixture reducing catalyst of 95vol% nitrogen, reduction
Maximum temperature be 260 DEG C.When constant temperature reduction 4 is small at 260 DEG C.After cooling, catalyst is obtained.Form, urge through Instrumental Analysis
Agent composition is as follows：
(1) copper, copper is in terms of metallic state, mass percentage content 5.1%；(2) magnesium, converts and is calculated for metallic state, quality
Degree is 1.8%；(3) cerium, converts and is calculated for metallic state, mass percentage content 3.9%；(4) chromium, is converted as gold
Belong to state, mass percentage content 2.0%；(5) alumina support, except metallic state and the content of the load component of metal oxidation state
Outer surplus.
Comparative example 1
From Zhejiang Xin Hua Chemical Co., Ltd.s obtain industry palladium-resin catalyst.
Embodiment 2
168.9 grams of copper nitrates, 1.9 grams of magnesium nitrates and 18.6 grams of cerous nitrates are dissolved in 442 grams of water in beaker, are made
Aqueous solution I.215.3 grammes per square metre ammonium chromates are dissolved in 500 grams of water in another beaker, aqueous solution II is made.Stirring and
At 70 DEG C, ammonium dichromate aqueous solution II is poured into the beaker of aqueous solution I, be then titrated to instead with 30wt% aqueous sodium carbonates
The pH value for answering liquid is 7.1.Then 542 grams of Ludox are added.Ludox is produced by Shandong marine chemical industry Co., Ltd, model
JN-30。
Then when aging 4 is small at 80 DEG C, then filters and wash, until sodium ions content is less than 0.05%.
It is dry, it is granulated, then the Roasting Decomposition at 380 DEG C.Finally beat piece is into graininess, particle diameter
Then according to temperature-programmed mode 5vol% hydrogen and the gaseous mixture reducing catalyst of 95vol% nitrogen, reduction
Maximum temperature be 260 DEG C.When constant temperature reduction 4 is small at 260 DEG C.After cooling, catalyst is obtained.Form, urge through Instrumental Analysis
Agent composition is as follows：
(1) copper, copper is in terms of metallic state, mass percentage content 14.8%；(2) magnesium, converts and is calculated for metallic state, quality
Degree is 0.06%；(3) cerium, converts and is calculated for metallic state, mass percentage content 2.0%；(4) chromium, converts and is
Metallic state, mass percentage content 14.8%；(5) silica supports, except the load component of metallic state and metal oxidation state
Content outside surplus.
Embodiment 3
114 grams of copper nitrates, 12.3 grams of calcium nitrate and 0.93 gram of cerous nitrate are dissolved in 297 grams of water in beaker, are made
Aqueous solution I.145.4 grammes per square metre ammonium chromates are dissolved in 340 grams of water in another beaker, aqueous solution II is made.Stirring and
At 70 DEG C, ammonium dichromate aqueous solution II is poured into the beaker of aqueous solution I, be then titrated to instead with 30wt% aqueous sodium carbonates
The pH value for answering liquid is 7.3.Then 148.6 grams of boehmites and 346.7 grams of Ludox are added.Boehmite is by three doses of Jiangsu
Industrial Co., Ltd. produces, specific surface area 290m2/ g, pore volume 0.9mL/g.Ludox is by Shandong marine chemical industry Co., Ltd
Production, model JN-30.
Then when aging 4 is small at 85 DEG C, then filters and wash, until sodium ions content is less than 0.05%.
It is dry, it is granulated, then the Roasting Decomposition at 380 DEG C.Finally beat piece is into graininess, particle diameter
Then according to temperature-programmed mode 5vol% hydrogen and the gaseous mixture reducing catalyst of 95vol% nitrogen, reduction
Maximum temperature be 260 DEG C.When constant temperature reduction 4 is small at 260 DEG C.After cooling, catalyst is obtained.Form, urge through Instrumental Analysis
Agent composition is as follows：
(1) copper, copper is in terms of metallic state, mass percentage content 10%；(2) calcium, converts and is calculated for metallic state, quality hundred
It is 1.0% to divide than content；(3) cerium, converts and is calculated for metallic state, mass percentage content 0.1%；(4) chromium, is converted as metal
State, mass percentage content 10%；(5) aluminium oxide-silicon oxide complex carrier, the two mass ratio are about 1:1, except metallic state and
Surplus outside the content of the load component of metal oxidation state.
Embodiment 4
79.9 grams of copper nitrates, 31.7 grams of magnesium nitrates, 18.6 grams of cerous nitrates and 101.8 grammes per square metre ammonium chromates are dissolved in beaker
In 350 grams of water, aqueous solution is made.
Mediated with 500 grams of boehmites, be extruded into the thick bars of 4mm, drying, 500 DEG C of roasting acquisition alumina supports.Pinching
It is modified to carry out carrier acid that 10 milliliters of phosphoric acid and 20 milliliters of sulfuric acid are added during conjunction.Boehmite is by three doses of the Jiangsu limited public affairs of industry
Department's production, specific surface area 290m2/ g, pore volume 0.9mL/g.
230 grams of carriers are taken, aqueous solution prepared above is immersed on carrier at twice, it is dry every time after dipping, 350
DEG C Roasting Decomposition.
Then according to temperature-programmed mode 5vol% hydrogen and the gaseous mixture reducing catalyst of 95vol% nitrogen, reduction
Maximum temperature be 260 DEG C.When constant temperature reduction 4 is small at 260 DEG C.After cooling, catalyst is obtained.Form, urge through Instrumental Analysis
Agent composition is as follows：
(1) copper, copper is in terms of metallic state, mass percentage content 7%；(2) magnesium, converts and is calculated for metallic state, quality hundred
It is 1.0% to divide than content；(3) cerium, converts and is calculated for metallic state, mass percentage content 2%；(4) chromium, is converted as metal
State, mass percentage content 7%；(5) alumina support, in addition to the content of metallic state and the load component of metal oxidation state
Surplus.
Embodiment 5
The present embodiment is evaluating catalyst example.
By Catalyst packing in the isothermal fixed bed reactors that oil bath controls, acetone is through measuring pump-metered and gaseous mass
The hydrogen of flowmeter control metering is mixed into preheater, and acetone vaporization, subsequently into reactor, flows through catalyst bed, pass through
Condensation, dehydration and hydrogenation serial reaction, reaction condition occur for catalyst effect：160 DEG C of reaction temperature, reaction pressure
1.0MPa, air speed 0.5h-1, hydrogen and acetone material amount ratio 3:1.
The catalyst of comparative example 1 is evaluated as：110 DEG C of reaction temperature, reaction pressure 1.0MPa, air speed 0.5h-1, hydrogen with
The ratio 3 of the amount of the material of acetone:1.
Result of the test such as table 1 below.
1 result of the test of table
As can be seen from Table 1, catalyst of the invention has higher compared to the palladium-resin catalyst of comparative example 1
Conversion ratio, can be with by-product methyl isobutyl carbinol and isopropanol while methyl iso-butyl ketone (MIBK) is produced, and isopropanol is
Preferable low molecule solvent, the heavy constituent of generation can be rinsed, maintain the stability of catalyst from bed.From one way
Conversion sees that the yield of methyl iso-butyl ketone (MIBK) is higher than the palladium-resin catalyst of comparative example 1.In addition, the catalyst of the present invention carries out
1000 it is small when stability assessment experiment, show preferable stability.
Claims (7)
- A kind of 1. catalyst of one-step method coproduction 4-methyl-2 pentanone and 4- methyl -2- amylalcohols, it is characterised in that the catalysis Agent includes carrier and load component copper, alkaline-earth metal, cerium and chromium, wherein alkaline-earth metal exist in the form of an oxide.
- 2. the catalyst of one-step method coproduction 4-methyl-2 pentanone as claimed in claim 1 and 4- methyl -2- amylalcohols, its feature It is, is counted using the mass percent of the catalyst as 100%, the catalyst includes consisting of：(1) copper, for copper in terms of metallic state, mass percentage content is 5%~15%；(2) alkaline-earth metal, converts and is calculated for metallic state, and mass percentage content is 0.05%~2%；(3) cerium, for cerium in terms of metallic state, mass percentage content is 0.1%~4%；(4) chromium, converts and is calculated for metallic state, and mass percentage content is 2%~15%；(5) carrier, the surplus in addition to the content of metallic state and the load component of metal oxidation state.
- 3. the catalyst of one-step method coproduction 4-methyl-2 pentanone as claimed in claim 1 or 2 and 4- methyl -2- amylalcohols, it is special Sign is that the alkaline-earth metal in the copper-based catalysts is one or both of magnesium and calcium.
- 4. the catalyst of one-step method coproduction 4-methyl-2 pentanone as claimed in claim 1 and 4- methyl -2- amylalcohols, its feature It is, the carrier is aluminium oxide, silica, aluminium oxide-silicon oxide complex carrier or molecular sieve.
- 5. the catalyst of one-step method coproduction 4-methyl-2 pentanone as claimed in claim 4 and 4- methyl -2- amylalcohols, its feature It is, the aluminium oxide is the modified aluminium oxide of acid or the aluminium oxide of alkali modification.
- 6. the catalyst of one-step method coproduction 4-methyl-2 pentanone as claimed in claim 4 and 4- methyl -2- amylalcohols, its feature It is, the silica is the modified silica of acid or the silica of alkali modification.
- 7. the catalyst of one-step method coproduction 4-methyl-2 pentanone as claimed in claim 4 and 4- methyl -2- amylalcohols, its feature It is, the oxidation of aluminium oxide-silicon oxide complex carrier or alkali modification that the aluminium oxide-silicon oxide complex carrier is modified for acid Aluminium-silica complex carrier.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110871073A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Catalyst for methyl isobutyl ketone high-space-velocity hydrogenation, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081937A (en) * | 1992-08-13 | 1994-02-16 | 中国石油化工总公司抚顺石油化工研究院 | The catalyzer and the method for making of Virahol synthesize methyl-isobutyl ketone/diisobutyl ketone |
| CN1108151A (en) * | 1994-12-22 | 1995-09-13 | 南开大学 | Catalyst for hydrogenation of acetone to synthesize methyl-isobutyl ketone, and its prepn. method |
| CN1255482A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for preparing isopropanol by hydrogenation of acetone |
| WO2004065305A1 (en) * | 2003-01-13 | 2004-08-05 | University Of Dayton | Non-toxic corrosion-protection pigments based on manganese |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN103420792A (en) * | 2012-05-14 | 2013-12-04 | 浙江新化化工股份有限公司 | Combined production method of isopropanol and methyl isobutyl ketone |
-
2016
- 2016-10-13 CN CN201610892292.3A patent/CN107930640B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081937A (en) * | 1992-08-13 | 1994-02-16 | 中国石油化工总公司抚顺石油化工研究院 | The catalyzer and the method for making of Virahol synthesize methyl-isobutyl ketone/diisobutyl ketone |
| CN1108151A (en) * | 1994-12-22 | 1995-09-13 | 南开大学 | Catalyst for hydrogenation of acetone to synthesize methyl-isobutyl ketone, and its prepn. method |
| CN1255482A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for preparing isopropanol by hydrogenation of acetone |
| WO2004065305A1 (en) * | 2003-01-13 | 2004-08-05 | University Of Dayton | Non-toxic corrosion-protection pigments based on manganese |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN103420792A (en) * | 2012-05-14 | 2013-12-04 | 浙江新化化工股份有限公司 | Combined production method of isopropanol and methyl isobutyl ketone |
Non-Patent Citations (1)
| Title |
|---|
| 申延明等: "Cu-MgO/γ-Al2O3丙酮一步法合成甲基异丁基酮", 《沈阳化工学院学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110871073A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Catalyst for methyl isobutyl ketone high-space-velocity hydrogenation, preparation method and application |
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