CN1594259A - Method for producing cyclopentanone, cyclopentanol - Google Patents
Method for producing cyclopentanone, cyclopentanol Download PDFInfo
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- CN1594259A CN1594259A CN 200410020790 CN200410020790A CN1594259A CN 1594259 A CN1594259 A CN 1594259A CN 200410020790 CN200410020790 CN 200410020790 CN 200410020790 A CN200410020790 A CN 200410020790A CN 1594259 A CN1594259 A CN 1594259A
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Abstract
The invention relates to a process for producing cyclopentanone and cyclopentanol by using adipic acid as the main raw material, wherein the further self-polymerization for creating high boiling point substance of the cyclopentanone is reduced at the presence of catalyst, thus increasing the yield of cyclopentanone.
Description
One, technical field: the present invention relates to a kind of hexanodioic acid that is applicable to is the production method that main raw material generates cyclopentanone, cyclopentanol.
Two, background technology: cyclopentanone is important fine chemical material, and it is the basic material of preparation Jasmin Chemicals spices, and field of medicaments can prepare anxiolytic buspirone etc.; Cyclopentanone has good solubility property to various resins, is used widely as solvent in electron trade, and whole world annual requirement reaches ten thousand tons.
Japanese Patent JP:2001 335,527, JP:2002 097,166, German patent DE: 3,6,38,005 usefulness petrochemical compleies oil refining by product carbon, five preparation cyclopentanone, this method technical process is long, by product is many, purification difficult, economic benefit is low.
European patent EP 0626363 is a main raw material with the hexanodioic acid, is catalyzer with the borax, prepares cyclopentanone under the high boiling solvent condition, cyclopentanone productive rate 91.5%; European patent EP 0626364 is a main raw material with the hexanodioic acid, is catalyzer with the tertiary sodium phosphate, prepares cyclopentanone under the high boiling solvent condition, cyclopentanone productive rate 92%; After these two kinds of methods use the tank reactor hexanodioic acid to generate cyclopentanone, cyclopentanone need be from the reaction soln internal divergence to the surface, cyclopentanone continues reaction generation 2-cyclopentylidene cyclopentanone and polymer in the high temperature high boiling solvent, under the catalyzer condition in diffusion process, increase polymer increase along with the reaction times, material viscosity rises in the reactor, make the cyclopentanone of generation can not in time be diffused into the reaction soln surface and steamed, the cyclopentanone yield is descended; Make reaction stirring system cisco unity malfunction and causing stop to produce simultaneously, solving with the hexanodioic acid is that to produce the further auto-polymerization reaction generation high boiling substance that reduces cyclopentanone in the cyclopentanone process under the catalyzer condition be the problem of this field common concern and research to main raw material.
Cyclopentanol is used for preparation treatment oedema and vascular hypertension tsiklometiazid [742-20-1].Cyclopentanol generates bromocyclopentane through bromo, bromocyclopentane again with the diethyl malonate effect, obtain the cyclopentyl diethyl malonate, get NSC 60134 [1123-00-8] through hydrolysis, decarboxylation again, again through reduce Cyclopentylacetaldehyde, synthetic thus tsiklometiazid.Cyclopentanol is through dehydration preparation cyclopentenes, and cyclopentenes is used to prepare ketamine, and novel non-veronal intravenous anesthetic has good analgesia usefulness.Cyclopentanol and aspartic acid effect generate cyclopentanol asparagus fern acid esters, generate the conjugation acid esters with the conjugate acid effect, generate the cyclopentanol fatty acid ester with the lipid acid effect, and they all have important biochemical medical functions, are indispensable in medicine industry.
It is lower that aluminum isopropylate changes H-H reaction system cyclopentanol yield, Claudio Bianchini and MakotoShibagaki have studied Ru, Os complex compound and Zir compound respectively and have reached 100% respectively as changeing hydrogen catalyst production cyclopentanol selectivity, but Zir compound catalyst consumption is big, Ru and Os belong to precious metal, and industrialization all acquires a certain degree of difficulty.Cyclopentanone hydrogenation system cyclopentanol can be by NaBH
4, the boride of Zn, Al/Hg aluminium amalgam, potassium+18 crown ethers-6, Hydrous Zirconnium Oxide, wherein the boride of Zn prepares the cyclopentanol transformation efficiency and reaches 100%, but needs low temperature, is difficult to industrialization, utilizes cyclopentanone at Ni, Cu/Al
2O
3Shortening system cyclopentanol on the catalyzer, cost is low, satisfies in the domestic and international pharmaceutical industry the phenomenon in short supply of cyclopentanol, and economic benefit is obvious.
Three, summary of the invention:
1, goal of the invention: the invention provides a kind of production method for preparing cyclopentanone by hexanodioic acid, it is that main raw material is produced the further auto-polymerization reaction generation high boiling substance that reduces cyclopentanone in the cyclopentanone process under the catalyzer condition that its purpose is to solve hexanodioic acid, thereby improve the yield of cyclopentanone, guarantee that effectively production unit normally moves; Simultaneously with the cyclopentanone that generates at Ni, Cu/Al
2O
3Shortening system cyclopentanol on the catalyzer, thus the production method of the cyclopentanol of a kind of high yield, highly selective is provided.
2, technical scheme: main technical schemes of the present invention is achieved in that
A kind of cyclopentanone, the production method of cyclopentanol, it is characterized in that adopting following processing step: with hexanodioic acid, high boiling solvent is made into hexanodioic acid high boiling solvent mixture by weight 1～10: 1～10 ratio, make the hexanodioic acid high boiling solvent mixture temperature that is made into rise to 180～300 ℃, stir, make the solid adipic acid fusion, be dissolved in the high boiling solvent uniformly, constitute the mixture of high boiling solvent fusion hexanodioic acid, with pump the mixture of high boiling solvent fusion hexanodioic acid being sent into temperature is 180～300 ℃ catalytic tower, beds is housed in the catalytic tower, loaded solid appendix catalyzer in the beds, high boiling solvent fusion hexanodioic acid reacts beds when catalytic tower is passed through from top to bottom, the cyclopentanone that reaction the generates beds that speeds away, enter the cyclopentanone condenser from the lateral space of beds, it is standby to be condensed into liquid cyclopentanone crude product; Effusive high boiling solvent and the unreacted a small amount of hexanodioic acid ratio by weight 1～10: 1～10 is made into hexanodioic acid high boiling solvent mixture and recycles at the bottom of the reaction tower; Above-mentioned liquid cyclopentanone crude product contains water and trace impurity, gets industrial first grade cyclopentanone through rectification process.
High boiling solvent refers to boiling point and is higher than following one or more mixtures of 300 ℃: hydrogenated terphenyl, biphenyl oil, biphenyl ether, machine oil, dioctyl phthalate (DOP), the two benzoic ethers of glycol ether.
Described solid appendix catalyzer refers to water, the catalyst activity component is made the catalyst activity component aqueous solution by weight 100～1000: 1～50 ratio, press solid catalyst carrier, the ratio of the weight ratio 100～1000: 1～50 of catalyst activity component adds support of the catalyst in the rotatory evaporator, 90～150 ℃ of temperature, under pressure 0.01～0.1Mpa condition the catalyst activity component aqueous solution was uniformly sprayed the carried catalyst that must adsorb the catalyst activity component on support of the catalyst in 3～20 hours, the carried catalyst that has adsorbed the catalyst activity component was got solid appendix catalyzer in 3～8 hours 260～600 ℃ of roastings.
Described solid catalyst carrier refers to granular active carbon, particulate state aluminium sesquioxide, particle silica gel, and cylinder shape catalyst carrier refers to diameter 1.2～4.0mm, long 3～8mm, surface-area 1000m
2～1300m
2The carrier of/g; The sheet catalyst carrier refers to thickness 1.0～2.0mm, long 4～8mm, wide 4～8mm, surface-area 1000m
2～1300m
2The carrier of/g.
Described catalyst activity component refers to the mixture of a kind of compound or multiple compound: a kind of compound in borax, tertiary sodium phosphate, Tripotassium phosphate, lead phosphate, hydrated barta, aluminium hydroxide, calcium hydroxide, Strontium carbonate powder, lithium hydroxide, molybdic oxide, three stannic oxide, vanadic acid sodium, potassium hydroxide, the lithium hydroxide, the mixture of two kinds of compounds or the mixture of multiple compound;
Described catalyst reaction tower refers to the cylindrical container of the high 3m～10m of diameter 500mm～2000mm, the tower tray of 3～20 layers of horizontal positioned is installed in the tower, load catalyzer in the tower tray and constitute beds, tray diameter is than the little 100～300mm of tower internal diameter, it is the aperture of 3～5mm that each tower tray backplane has diameter, high 10～the 100mm of tower tray, every two-layer tray spacing 150～300mm, load solid appendix catalyzer in the tower tray by claim 3 preparation, the shape of tower tray guarantee high boiling solvent hexanodioic acid melted blend from the lastblock tower tray with flow down after solid appendix catalyzer fully contacts, next piece tower tray of flowing through, the hexanodioic acid of last high boiling solvent and traces of unreacted flow at the bottom of the reaction tower, in glass lined reaction vessel, allocate hexanodioic acid by pump delivery again into, recycle.
A kind of cyclopentanone, the production method of cyclopentanol, it is characterized in that adopting following processing step: the solid catalysis hydrogenation catalyst is filled in diameter 20～45mm, length is in the single hose or multitube catalytic hydrogenation device of 1～10m, the filling height 0.1～10m of catalyst layer, reactor temperature maintains 130～200 ℃, hydrogen pressure maintains 0.1～1.0MPa, 0.2～20000 cubic metre of hydrogen flow rate per hour, enter the catalytic hydrogenation device from the lower end, cyclopentanone is entered the catalytic hydrogenation device from the lower end, 0.1～1000 kilogram of the flow velocity of cyclopentanone per hour, the catalytic hydrogenation product flows out from catalytic hydrogenation device upper end, and effluent gets content greater than 99.5% cyclopentanol through rectifying.
The preparation method of described solid catalysis hydrogenation catalyst adopts following processing step: with cupric nitrate, nickelous nitrate, aluminum nitrate, water is by weight 1～5: 1～5: 1～30: 100～1000 ratio is made the aqueous solution, stirring at room, drip 10～25% ammoniacal liquor, make above-mentioned solution pH value reach 7～8, make above-mentioned solution generate precipitation, precipitation is deviate from moisture through whizzer, wash with water and be precipitated to neutrality, precipitation is made diameter 1.0～3.0mm, the deposit seeds of length 3～8mm, deposit seeds was dried 1～3 hour under 100～300 ℃ of nitrogen gas stream, 450～800 ℃ of roastings got non-activated solid catalysis hydrogenation catalyst in 5～8 hours, the non-activated solid catalysis hydrogenation catalyst of above-mentioned preparation is added in the catalytic hydrogenation device, feed 0.01～1.0Mpa hydrogen stream and carry out catalyst activation, 100～110 ℃ of activation temperatures 1～5 hour, 150～190 ℃ 1～5 hour, 230～240 ℃ 1～5 hour, 200～260 ℃ 3～120 hours, be cooled to room temperature, get activatory solid catalysis hydrogenation catalyst.
3, advantage and effect
(1) prepared cyclopentanone, cyclopentanol meets the requirement of perfume industry, pharmaceutical industry;
(2) technology simple, be applicable to continuous industryization, cost is low, economic benefit is high;
(3) catalyst life is long;
(4) high boiling solvent long service life.
Four, embodiment: following the present invention will be further described in conjunction with the embodiments, but not only comprise following examples:
Embodiment one:
The cyclopentanone production technique is as follows:
With hexanodioic acid, hydrogenated terphenyl is made into hexanodioic acid～hydrogenated terphenyl mixture by weight 1: 8 ratio, make the hexanodioic acid～hydrogenated terphenyl mixture temperature that is made into rise to 260 ℃, stir, make the solid adipic acid fusion, be dissolved in the mixture that constitutes hydrogenated terphenyl～fusion hexanodioic acid in the hydrogenated terphenyl uniformly, with pump the mixture of hydrogenated terphenyl～fusion hexanodioic acid is sent into the catalytic tower that temperature is 260 degree, beds is housed in the catalytic tower, loaded solid appendix catalyzer in the beds, hydrogenated terphenyl～fusion hexanodioic acid reacts beds when catalytic tower is passed through from top to bottom, the cyclopentanone that reaction the generates beds that speeds away enters the cyclopentanone condenser from the lateral space of beds, and it is standby to be condensed into liquid cyclopentanone crude product; Effusive high boiling solvent and unreacted a small amount of hexanodioic acid are made into hexanodioic acid～hydrogenated terphenyl mixture by weight 1: 8 ratio and recycle at the bottom of the reaction tower; Drop into the 1460Kg hexanodioic acid and get the 807Kg cyclopentanone, yield 96%; Above-mentioned liquid cyclopentanone crude product contains water and trace impurity, gets industrial first grade cyclopentanone through rectification process;
Solid appendix catalyzer refers to makes trisodium phosphate aqueous solution with water, tertiary sodium phosphate by weight 1000: 30 ratio, 1000: 30 ratio of weight ratio in support of the catalyst, tertiary sodium phosphate adds support of the catalyst in the rotatory evaporator, 120 ℃ of temperature, under the pressure 0.03Mpa condition catalyst activity component aqueous solution was uniformly sprayed the carried catalyst that must adsorb the catalyst activity component on support of the catalyst in 15 hours, the carried catalyst that has adsorbed the catalyst activity component was got solid appendix catalyzer in 6 hours 450 ℃ of roastings; Solid catalyst carrier refers to the cylindrical pellet gac, and the cylinder shape catalyst carrier particle refers to diameter 1.2～4.0mm, long 3～8mm, surface-area 1000m
2～1200m
2/ g;
Above-mentioned catalyst reaction tower refers to the cylindrical container of the high 6m of diameter 800mm, the tower tray of 10 layers of horizontal positioned is installed in the tower, load above-mentioned catalyzer in the tower tray and constitute beds, tray diameter is than the little 200mm of tower internal diameter, it is the aperture of 3mm that each tower tray backplane has diameter, the high 90mm of tower tray, the solid appendix catalyzer of the above-mentioned preparation of filling in the every two-layer tray spacing 260mm, tower tray;
The production technique of cyclopentanol is as follows:
The solid catalysis hydrogenation catalyst is filled in diameter 32mm, length is in the multitube catalytic hydrogenation device of 3m, the filling height 2.6m of catalyst layer, reactor temperature maintains 150 ℃, hydrogen pressure maintains 0.4MPa, 16 cubic metres of hydrogen flow rates per hour, enter the catalytic hydrogenation device from the lower end, cyclopentanone is entered the catalytic hydrogenation device from the lower end, 12 kilograms of the flow velocitys of cyclopentanone per hour, the catalytic hydrogenation product flows out from catalytic hydrogenation device upper end, effluent through rectifying get cyclopentanol, cyclopentanol content is greater than 99.5% after testing; The selectivity that cyclopentanone is converted into cyclopentanol is 100%;
The preparation method of above-mentioned solid catalysis hydrogenation catalyst: with cupric nitrate, nickelous nitrate, aluminum nitrate, water was by weight 1: 3: 8: 100 ratio is made the aqueous solution, stirring at room, drip 20% ammoniacal liquor, make above-mentioned solution pH value reach 7.8, make above-mentioned solution generate precipitation, precipitation is deviate from moisture through whizzer, wash with water and be precipitated to neutrality, precipitation is made diameter 3.0mm, the deposit seeds of length 6～8mm, deposit seeds was dried 3 hours under 260 degree nitrogen gas stream, 500 degree roastings got non-activated solid catalysis hydrogenation catalyst in 6 hours, the non-activated solid catalysis hydrogenation catalyst of above-mentioned preparation is added in the catalytic hydrogenation device, feed the 0.1Mpa hydrogen stream and carry out catalyst activation, activation temperature 100～110 degree 3 hours, 150～190 degree 3 hours, 230～240 degree 3 hours, 200～260 degree 20 hours, the cooling room temperature gets activatory solid catalysis hydrogenation catalyst.
Claims (8)
1, a kind of cyclopentanone, the production method of cyclopentanol, it is characterized in that adopting following processing step: with hexanodioic acid, high boiling solvent is made into hexanodioic acid high boiling solvent mixture by weight 1～10: 1～10 ratio, make the hexanodioic acid high boiling solvent mixture temperature that is made into rise to 180～300 ℃, stir, make the solid adipic acid fusion, be dissolved in the high boiling solvent uniformly, constitute the mixture of high boiling solvent fusion hexanodioic acid, with pump the mixture of high boiling solvent fusion hexanodioic acid being sent into temperature is 180～300 ℃ catalytic tower, beds is housed in the catalytic tower, loaded solid appendix catalyzer in the beds, high boiling solvent fusion hexanodioic acid reacts beds when catalytic tower is passed through from top to bottom, the cyclopentanone that reaction the generates beds that speeds away, enter the cyclopentanone condenser from the lateral space of beds, it is standby to be condensed into liquid cyclopentanone crude product; Effusive high boiling solvent and the unreacted a small amount of hexanodioic acid ratio by weight 1～10: 1～10 is made into hexanodioic acid high boiling solvent mixture and recycles at the bottom of the reaction tower; Above-mentioned liquid cyclopentanone crude product contains water and trace impurity, gets industrial first grade cyclopentanone through rectification process.
2, according to a kind of cyclopentanone described in the claim 1, the production method of cyclopentanol, it is characterized in that high boiling solvent refers to boiling point and is higher than following one or more mixtures of 300 ℃: hydrogenated terphenyl, biphenyl oil, biphenyl ether, machine oil, dioctyl phthalate (DOP), the two benzoic ethers of glycol ether.
3, according to a kind of cyclopentanone described in the claim 1, the production method of cyclopentanol, it is characterized in that described solid appendix catalyzer refers to water, the catalyst activity component is made the catalyst activity component aqueous solution by weight 100～1000: 1～50 ratio, press solid catalyst carrier, the ratio of the weight ratio 100～1000: 1～50 of catalyst activity component adds support of the catalyst in the rotatory evaporator, 90～150 ℃ of temperature, under pressure 0.01～0.1Mpa condition the catalyst activity component aqueous solution was uniformly sprayed the carried catalyst that must adsorb the catalyst activity component on support of the catalyst in 3～20 hours, the carried catalyst that has adsorbed the catalyst activity component was got solid appendix catalyzer in 3～8 hours 260～600 ℃ of roastings.
4, according to a kind of cyclopentanone described in the claim 1, the production method of cyclopentanol, it is characterized in that described solid catalyst carrier refers to granular active carbon, particulate state aluminium sesquioxide, particle silica gel, cylinder shape catalyst carrier refers to diameter 1.2～4.0mm, long 3～8mm, surface-area 1000m
2～1300m
2The carrier of/g; The sheet catalyst carrier refers to thickness 1.0～2.0mm, long 4～8mm, wide 4～8mm, surface-area 1000m
2～1300m
2The carrier of/g.
5, the production method of a kind of cyclopentanone according to claim 3, cyclopentanol is characterized in that described catalyst activity component refers to the mixture of a kind of compound or multiple compound: a kind of compound in borax, tertiary sodium phosphate, Tripotassium phosphate, lead phosphate, hydrated barta, aluminium hydroxide, calcium hydroxide, Strontium carbonate powder, lithium hydroxide, molybdic oxide, three stannic oxide, vanadic acid sodium, potassium hydroxide, the lithium hydroxide, the mixture of two kinds of compounds or the mixture of multiple compound;
6, a kind of cyclopentanone according to claim 1, the production method of cyclopentanol, it is characterized in that described catalyst reaction tower refers to the cylindrical container of the high 3m～10m of diameter 500mm～2000mm, the tower tray of 3～20 layers of horizontal positioned is installed in the tower, load catalyzer in the tower tray and constitute beds, tray diameter is than the little 100～300mm of tower internal diameter, it is the aperture of 3～5mm that each tower tray backplane has diameter, high 10～the 100mm of tower tray, every two-layer tray spacing 150～300mm, load solid appendix catalyzer in the tower tray by claim 3 preparation, the shape of tower tray guarantee high boiling solvent hexanodioic acid melted blend from the lastblock tower tray with flow down after solid appendix catalyzer fully contacts, next piece tower tray of flowing through, the hexanodioic acid of last high boiling solvent and traces of unreacted flow at the bottom of the reaction tower, in glass lined reaction vessel, allocate hexanodioic acid by pump delivery again into, recycle.
7, a kind of cyclopentanone, the production method of cyclopentanol, it is characterized in that adopting following processing step: the solid catalysis hydrogenation catalyst is filled in diameter 20～45mm, length is in the single hose or multitube catalytic hydrogenation device of 1～10m, the filling height 0.1～10m of catalyst layer, reactor temperature maintains 130～200 ℃, hydrogen pressure maintains 0.1～1.0MPa, 0.2～20000 cubic metre of hydrogen flow rate per hour, enter the catalytic hydrogenation device from the lower end, cyclopentanone is entered the catalytic hydrogenation device from the lower end, 0.1～1000 kilogram of the flow velocity of cyclopentanone per hour, the catalytic hydrogenation product flows out from catalytic hydrogenation device upper end, and effluent gets content greater than 99.5% cyclopentanol through rectifying.
8, a kind of cyclopentanone according to claim 7, the production method of cyclopentanol, the preparation method who it is characterized in that described solid catalysis hydrogenation catalyst adopts following processing step: with cupric nitrate, nickelous nitrate, aluminum nitrate, water is by weight 1～5: 1～5: 1～30: 100～1000 ratio is made the aqueous solution, stirring at room, drip 10～25% ammoniacal liquor, make above-mentioned solution pH value reach 7～8, make above-mentioned solution generate precipitation, precipitation is deviate from moisture through whizzer, wash with water and be precipitated to neutrality, precipitation is made diameter 1.0～3.0mm, the deposit seeds of length 3～8mm, deposit seeds was dried 1～3 hour under 100～300 ℃ of nitrogen gas stream, 450～800 ℃ of roastings got non-activated solid catalysis hydrogenation catalyst in 5～8 hours, the non-activated solid catalysis hydrogenation catalyst of above-mentioned preparation is added in the catalytic hydrogenation device, feed 0.01～1.0Mpa hydrogen stream and carry out catalyst activation, 100～110 ℃ of activation temperatures 1～5 hour, 150～190 ℃ 1～5 hour, 230～240 ℃ 1～5 hour, 200～260 ℃ 3～120 hours, be cooled to room temperature, get activatory solid catalysis hydrogenation catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044226A (en) * | 2012-12-26 | 2013-04-17 | 淮安万邦香料工业有限公司 | Method for preparing cyclopentanone from adipic acid |
| CN105418342A (en) * | 2015-11-09 | 2016-03-23 | 贝利化学（张家港）有限公司 | High-temperature decarboxylation method |
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| CN105713356B (en) | 2016-03-07 | 2017-05-31 | 杨红梅 | A kind of Biodegradable polyester composition |
| CN105585825A (en) | 2016-03-07 | 2016-05-18 | 杨红梅 | Biodegradable polyester composition |
| CN105585824A (en) | 2016-03-07 | 2016-05-18 | 金发科技股份有限公司 | Biodegradable polyester composition |
| CN105585826A (en) | 2016-03-07 | 2016-05-18 | 金发科技股份有限公司 | Biodegradable polyester composition |
| CN105585827A (en) | 2016-03-07 | 2016-05-18 | 金发科技股份有限公司 | Biodegradable polyester composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044226A (en) * | 2012-12-26 | 2013-04-17 | 淮安万邦香料工业有限公司 | Method for preparing cyclopentanone from adipic acid |
| CN105418342A (en) * | 2015-11-09 | 2016-03-23 | 贝利化学（张家港）有限公司 | High-temperature decarboxylation method |
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