CN106631691A - Method for preparing methallyl alcohol through acrylaldehyde selective hydrogenization - Google Patents
Method for preparing methallyl alcohol through acrylaldehyde selective hydrogenization Download PDFInfo
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- CN106631691A CN106631691A CN201611123365.9A CN201611123365A CN106631691A CN 106631691 A CN106631691 A CN 106631691A CN 201611123365 A CN201611123365 A CN 201611123365A CN 106631691 A CN106631691 A CN 106631691A
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- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention relates to a method for preparing methallyl alcohol through acrylaldehyde selective hydrogenization. The method mainly solves the problems of low production capability, low raw material conversion rate, low product selectivity and separation difficulty of catalysts and products in the prior art. The method adopts the technical scheme that the method of preparing methallyl alcohol through acrylaldehyde selective hydrogenization is used, acrylaldehyde and hydrogen gas are continuously introduced into a fixed bed reactor; under the catalyst reaction condition, the continuous catalysis selective hydrogenization reaction is performed; the generated product is subjected to gas-liquid separation and fractionating; then, a methallyl alcohol product and unreacted acrylaldehyde are obtained; the hydrogen gas obtained after the gas-liquid separation and the unreated acrylaldehyde obtained after the fractionating are cyclically used. The problems are well solved. The method can be used for preparing methallyl alcohol through acrylaldehyde selective hydrogenization.
Description
Technical field
The present invention relates to a kind of method that MAL selects Hydrogenation methallyl alcohol.
Background technology
Methallyl alcohol is a kind of important organic intermediate, for synthetic perfume, resin etc..With methallyl alcohol and ring
Oxidative ethane is Material synthesis methyl allyl alcohol polyoxyethylene ether (HPEG), can be made as high performance concrete water reducer of new generation
With the market demand is vigorous.
Polycarboxylate water-reducer segregation ester type (MPEG) and the big class of polyether-type (APEG/TPEG) two, polyether-type water reducer occurs
Though it is later, started production application from 2008 and start, in 2010 end of the year markets polyether-type water reducer more than 50%, development
Very fast, simple mainly due to the processing of polyether-type water reducer, stable performance, technical requirements are relatively low, application side
Just etc. factor is facilitated, it is contemplated that still there is larger development space in future.
In recent years polycarboxylic acid concrete water reducer demand speedup is always held at more than 20%.Polycarboxylate water-reducer in 2013
Polymeric monomer yield about reaches 570,000 tons.Therefore the methallyl alcohol conservative estimation in terms of being only used for water reducer just has 130,000 tons/year of left sides
It is right.
Because the country and people is to the gradually stronger of environmental consciousness, the chemical products of high-efficiency low-toxicity increasingly receive an acclaim,
Methallyl alcohol property is similar with allyl alcohol, and toxicity is less than allyl alcohol.In many fields, it can substitute allyl alcohol.Current state
The consumption figure (calculating according to epoxychloropropane consumption) of interior allyl alcohol is about 600,000 tons/year, if 50% can be substituted, methallyl alcohol
Demand will greatly promote.
Although domestic for methallyl alcohol market demand and production capacity etc. are not also clearly counted at present, only from for water
Mud water reducer and allyl alcohol is substituted analyzing, market potential is huge.
Traditional chlorohydrination produces 10,000 tons of methallyl alcohols with 14000 tons of chlorine, and chlorine is all changed into accessory substance and pollution
Thing, such as:Tert-butyl chloride, two iso-chlorobutanes, chloromethanes, sodium chloride, calcium chloride, hydrochloric acid etc., contain various chlorinations in accessory substance
Thing, it is impossible to as conforming articls sale.A large amount of alkali are used, a large amount of saliferous is produced, is utilized containing other muriatic waste water, and atom
Rate only has 30~40%.10000 tons of product will have tens of thousands of tons of reluctant solid waste, waste water.Propylene oxide by chlorohydrination exists
Used by restriction in national industry structural adjustment catalogues in 2011, chlorohydrination methallyl alcohol is because of manufacturing enterprise's small scale environmental protection
The difficulty of improvement is bigger, therefore a kind of cleaning of exploitation, methallyl alcohol production technology efficiently, environmentally friendly have highly important meaning
Justice.For example in Chinese patent CN101759528A introduce and hold water, solid base, 2- methallyl chlorides and polyethylene glycol in reaction
It is heated to reflux in device, by stratification, obtains in organic layer product methallyl alcohol.During using to high concentration alkali
The aqueous solution, produces saliferous solid waste that is a large amount of difficult and cannot recycling and waste water.
The content of the invention
The technical problem to be solved is that production capacity is less in prior art, feed stock conversion and product are selected
Property relatively low, catalyst be difficult to detached problem with product, there is provided a kind of new MAL selects Hydrogenation methallyl alcohol
Method.The method has higher larger production capacity, feed stock conversion and product selectivity, catalyst and product segregative
Advantage.
To solve the above problems, the technical solution used in the present invention is as follows:A kind of MAL selects Hydrogenation methyl
The method of allyl alcohol, MAL and hydrogen are continuously passed through in the fixed bed reactors equipped with catalyst, in certain reaction bar
Carry out continuous catalysis selective hydrogenation reaction under part, the product of generation obtain Jing after gas-liquid separation and rectifying methallyl alcohol product and
Unreacted MAL, the unreacted MAL obtained after gas-liquid separation hydrogen out and rectifying is looped back
With;
Wherein, the catalyst includes the first component, the second component, third component and carrier;First component be Cu,
The metal or oxide of the mixture of Ag or Cu and Ag, the second component is at least one metal or oxygen in Au, Ir, Ru and Pt
Compound, third component is at least one metal or oxide in La, In, Co, Sn, Fe, Mn, and carrier is MgO, TiO2、
Al2O3、SiO2, activated carbon, diatomite, ZrO2, ZnO, HY molecular sieve, at least one in ZSM-5 molecular sieve;Wherein, first group
Point mass content is 0.1~33%, and the mass content of the second component is 0.1~5%, the mass content of third component is 0.1~
5%, the mass content of carrier is 57~99.7%;
The reaction condition is:Solvent-free, the mol ratio of hydrogen/aldehyde is 1~60:1, reaction temperature is 30~250 DEG C, instead
Pressure is answered to be 0.2~4.0MPa, the mass space velocity of MAL is 0.1~5.0h-1。
In above-mentioned technical proposal, it is preferable that carry out selecting hydrogenation using hydrogen and remove heat, reaction raw materials are anti-through fixed bed
After answering device, the hydrogen that reactor outlet material Jing gas-liquid devices are isolated is recycled.
In above-mentioned technical proposal, it is preferable that the cylindrically shaped/cylindrical hollow of catalyst, five tooth balls or cloverleaf pattern,
2.0~4.0mm of catalyst diameter, length is 2.0~4.0mm.
In above-mentioned technical proposal, it is preferable that catalyst adopts infusion process, sol-gal process, deposition-precipitation method;Using dipping
When prepared by method:Using the salting liquid containing the first component as single-steeping liquid, impregnation concentration is 0.05~1.0M, then to contain
The salting liquid of two kinds or more promoter metal ions in the second component and third component is used as double-steeping liquid, impregnation concentration
For 0.05~0.5M;Or with simultaneously by one or two promoter metal ions in the first component, the second component and third component
Salting liquid impregnates as maceration extract, and carrier drying, roasting and reduction afterwards obtains required catalyst;Using collosol and gel legal system
When standby:The metal alkoxide or inorganic salts of the metal alkoxide or inorganic salts of carrier and each active component are sufficiently mixed into contact, are passed through
Hydrolytic condensation gradually becomes gel by colloidal sol, and through aging, dry, roasting catalyst precursor is obtained;Using deposition-precipitation method
During preparation:Carrier is dissolved in into certain aqueous solution stirring, certain density metal salt solution and aqueous slkali is configured, according to certain
Order adds carrier aqueous solution stirring, and reaches certain pH, and washing, filtering drying, roasting obtain catalyst precursor.
In above-mentioned technical proposal, it is preferable that add in metal salt solution selected from polyethylene glycol, lauryl sodium sulfate, gather
A kind of surfactant in vinylpyrrolidone, neopelex, surfactant concentration is 0~1.0M;It is described
Salt is sulfate, nitrate, acetate, the chloride of each metal active constituent:Catalyst needs dry, roasting and reduction, does
Dry temperature is 80~150 DEG C, and drying time is 8~24h;Sintering temperature is that roasting time is 4~12h at 250~600 DEG C;Also
Primordial Qi atmosphere is the mixed gas of hydrogen or hydrogen/nitrogen, and reduction pressure is 0.1~5MPa, temperature is 150~400 DEG C, goes back Primordial Qi
Body volume space velocity is 500~5000h-1, the recovery time be 3~30h.
The present invention selects hydrogenation technique, the raw material MAL and hydrogen Jing under uniform temperature and pressure using fixed bed
The lower production methallyl alcohol of proprietary selective hydrogenation catalyst effect is crossed, after unreacted MAL and the separated purification of hydrogen
Return hydrogenation reactor and be circulated utilization.The process is that a kind of green, pollution-free, atom utilization is high to be met now
The new process of socio-economic development.Unreacted hydrogen and MAL in the reaction process of the present invention, can pass through
The mode of reuse enters selective hydrogenation reaction device, so as to make full use of raw material MAL and hydrogen.Reaction process of the present invention
Middle raw material MAL is pure charging, is not added with any solvent, greatlys save energy consumption and separation costs.What the present invention was used
Catalyst, supporting process can obtain higher MAL conversion ratio and methallyl alcohol selectivity, achieve
Preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
Embodiment 1
Weigh 20g TiO2Carrier, is dissolved in a certain amount of copper-bath containing polyethylene glycol, and under normal temperature 12h is impregnated,
Then Cu/TiO is obtained in 80 DEG C of stirring and dryings2Presoma;By Cu/TiO2Presoma is dissolved in a certain amount of gold chloride and protochloride
12h is impregnated under the mixed liquor of tin, normal temperature, then in 80 DEG C of stirring and dryings.The sample for obtaining is dried into 24h, 600 DEG C of roastings at 80 DEG C
4h is burnt, loaded catalyst 33%Cu-0.1%Au-0.1%Sn/TiO is obtained2.Each component in the loaded catalyst of preparation
Content is weight/mass percentage composition, as follows.
Embodiment 2
Weigh 20g ZrO2Carrier, is dissolved in a certain amount of silver nitrate solution containing lauryl sodium sulfate, soaks under normal temperature
Stain 12h, then obtains precursor A g/ZrO in 80 DEG C of stirring and dryings2Presoma;By Ag/ZrO2Presoma is dissolved in a certain amount of chloride
Iridium acid and lanthanum nitrate hexahydrate, impregnate 12h, then in 80 DEG C of stirring and dryings under normal temperature.The sample for obtaining is dried into 8h at 150 DEG C,
250 DEG C of roasting 12h, obtain loaded catalyst 0.5%Ag-5%Ir-%5La/ZrO2。
Embodiment 3
20g ZnO carriers are weighed, a certain amount of silver nitrate solution containing polyvinylpyrrolidone is dissolved in, is impregnated under normal temperature
12h, then obtains precursor A g/ZnO presoma in 80 DEG C of stirring and dryings;Ag/ZnO presomas are dissolved in into a certain amount of ruthenic chloride
With 12h is impregnated under the mixed liquor of manganese nitrate, normal temperature, then in 80 DEG C of stirring and dryings.The sample for obtaining is dried into 16h at 115 DEG C,
425 DEG C of roasting 6h, obtain loaded catalyst 19%Ag-1%Ru-2%Mn/ZnO.
Embodiment 4
Weigh 20g HZSM-5 carriers, be dissolved in containing a certain amount of copper nitrate, chloroplatinic acid, cobalt nitrate, ferric nitrate the aqueous solution,
Ethylene glycol stirring is added in dipping solution, 12h is impregnated under normal temperature, then in 100 DEG C of stirring and dryings.By the sample for obtaining 120
DEG C 12h, 500 DEG C of roasting 3h are dried, obtain loaded catalyst 16.5%Cu-2%Pt-1%Co-1%Fe/HZSM-5.Implement
Example 5
Weigh 20g Al2O3Carrier, be dissolved in containing a certain amount of silver nitrate and copper nitrate, chloroplatinic acid, indium nitrate it is water-soluble
Liquid, adds dodecyl sodium sulfate stirring in dipping solution, 12h is impregnated under normal temperature, then in 100 DEG C of stirring and dryings.To obtain
Sample 12h, 450 DEG C of roasting 8h are dried at 100 DEG C, obtain loaded catalyst 15%Ag-2%Cu-1%Pt-2%In/
SiO2。
Embodiment 6
20g MgO carriers are weighed, the aqueous solution containing a certain amount of copper nitrate, gold chloride and lanthanum nitrate is dissolved in, is impregnated molten
Polyvinylpyrrolidone stirring is added in liquid, 12h is impregnated under normal temperature, then in 100 DEG C of stirring and dryings.The sample for obtaining is existed
120 DEG C are dried 12h, 500 DEG C of roasting 7h, obtain loaded catalyst 11%Cu-1%Au-1%La/MgO.
Embodiment 7
Sol-gal process prepares catalyst, by tetraethyl orthosilicate (Si (OC2H5)4) and copper nitrate, gold chloride, cobalt nitrate match somebody with somebody
Into solution, ammoniacal liquor is slowly added dropwise in above-mentioned solution, adjusts pH=8, be fully hydrolyzed generation colloidal sol, colloidal sol is dried into shape at 80 DEG C
Into gel.The sample for obtaining is dried into 12h, 400 DEG C of roasting 4h at 120 DEG C.Obtain catalyst 22%Cu-1%Au-1%Co/
SiO2。
Embodiment 8
20g diatomite supports are weighed, is dissolved under a certain amount of silver nitrate solution, normal temperature and is impregnated 12h, then in 80 DEG C of stirrings
Drying obtains precursor A g/ diatomite, precursor A g/ diatomite is dissolved in into a certain amount of ruthenic chloride, cobalt nitrate, stannous chloride molten
Liquid, and 0.5M polyvinylpyrrolidones are added, then obtain sample in 80 DEG C of stirring and dryings.The sample for obtaining is dry at 120 DEG C
Dry 12h, 400 DEG C of roasting 3h, obtain loaded catalyst 22%Ag-1.2%Ru-1.0%Co-1.0%Sn/ diatomite.
Embodiment 9
The precipitation method prepare catalyst, weigh 20g diatomite supports, are dissolved in containing a certain amount of copper nitrate, gold chloride and nitre
The aqueous solution of sour iron, manganese nitrate, stirring is warming up to 80 DEG C, continues to stir 30min, and the Na of 0.5M is added dropwise under stirring condition2CO3It is molten
Liquid, drips in 15~30min of control, and final pH is 8.5, constant temperature stirring 2h, aging 6h, sediment is filtered, is washed 3 times.
The sample for obtaining is dried into 12h, 400 DEG C of roasting 8h at 120 DEG C, loaded catalyst 15%Cu-2.0%Au-1%Fe- is obtained
1%Mn/ diatomite.
Comparative example 1
Weigh 20g SiO2, a certain amount of ammonium perrhenate and Chloroiridic Acid solution are dissolved in, after 80 DEG C of stirring and dryings, by what is obtained
Sample is dried 12h, 500 DEG C of roasting 7h at 120 DEG C, obtains loaded catalyst 2%Re-2%Ir/SiO2。
Above-described embodiment 1-9 and the catalyst compressing tablet of comparative example 1,5.0 grams of 20~40 mesh catalyst of screening are packed into solid
In fixed bed reactor, catalyst is in 1500h-1Under hydrogen gas space velocity and uniform temperature and under the time reduce.By raw material MAL
Reactor, 180 DEG C of controlling reaction temperature, reaction pressure 4.0MPa are entered with after hydrogen mixing preheating;The quality of MAL
Air speed is 1.0h-1, the mol ratio 40 of hydrogen/MAL.The results are shown in Table 1.
Each catalyst test result on the fixed bed reactors of table 1
Embodiment 10
MAL is added and is continuously passed through equipped with 22%Ag-1.2%Ru-1.0%Co-1.0%Sn/ after raw material storage tank
The hydrogenation reactor of diatomite catalyst.Fresh hydrogen and circulating hydrogen are respectively with the mol ratio 1 with MAL:1 and 1:1
Ratio is passed through in hydrogenation reactor.Hydrogenation reactor hydroconversion condition be 240 DEG C of reaction temperature, reaction pressure 0.8MPa, methyl-prop
Olefine aldehydr mass space velocity:0.2h-1.Material after reactor reaction is Jing after gas-liquid separator, and vapor phase hydrogen is fresh with what is be continuously replenished
Hydrogen is fed again into together in hydrogenation reactor, and liquid phase obtains methallyl alcohol and unreacted first Jing after rectifying into rectifying column
Base methacrylaldehyde, unreacted MAL enters hydrogenation reactor after separating.
The liquid product that analysis hydrogenation reactor outlet is collected:MAL conversion ratio 80.5%, methallyl alcohol choosing
Ze≤78.2%.Methallyl alcohol Chan product Chun Du≤99.5% that rectifying column rectifying is obtained, reaches top grade product grade.
Embodiment 11
MAL is added and is continuously passed through equipped with 22%Cu-1%Au-1%Co/SiO after raw material storage tank2Catalyst
Hydrogenation reactor.Fresh hydrogen and circulating hydrogen are respectively with the mol ratio 1.0 with MAL:1 and 49:1 ratio is passed through and adds
In hydrogen reactor.Hydrogenation reactor hydroconversion condition is 137 DEG C of reaction temperature, and reaction pressure 4.0MPa, MAL quality is empty
Speed:4.2h-1.Material after reactor reaction Jing after gas-liquid separator, vapor phase hydrogen together with the fresh hydrogen being continuously replenished again
In secondary feeding hydrogenation reactor, liquid phase obtains methallyl alcohol and unreacted MAL Jing after rectifying into rectifying column,
Unreacted MAL enters hydrogenation reactor after separating.
The liquid product that analysis hydrogenation reactor outlet is collected:MAL conversion ratio 82.3%, methallyl alcohol choosing
Ze≤79.2%.Methallyl alcohol Chan product Chun Du≤99.6% that rectifying column rectifying is obtained, reaches top grade product grade.
Embodiment 12
MAL is added and is continuously passed through equipped with 19%Ag-1%Ru-2%Mn/ZnO catalyst after raw material storage tank
Hydrogenation reactor.Fresh hydrogen and circulating hydrogen are respectively with the mol ratio 1.3 with MAL:1 and 28:1 ratio is passed through and adds
In hydrogen reactor.Hydrogenation reactor hydroconversion condition is 170 DEG C of reaction temperature, and reaction pressure 2.8MPa, MAL quality is empty
Speed:1.5h-1.Material after reactor reaction Jing after gas-liquid separator, vapor phase hydrogen together with the fresh hydrogen being continuously replenished again
In secondary feeding hydrogenation reactor, liquid phase obtains methallyl alcohol and unreacted MAL Jing after rectifying into rectifying column,
Unreacted MAL enters hydrogenation reactor after separating.
The liquid product that analysis hydrogenation reactor outlet is collected:MAL conversion ratio 85.7%, methallyl alcohol choosing
Ze≤72.3%.Methallyl alcohol Chan product Chun Du≤99.3% that rectifying column rectifying is obtained, reaches top grade product grade.
Embodiment 13
MAL is added and is continuously passed through equipped with 0.5%Ag-5%Ir-%5La/ZrO after raw material storage tank2Catalyst
Hydrogenation reactor.Fresh hydrogen and circulating hydrogen are respectively with the mol ratio 1.5 with MAL:1 and 35:1 ratio is passed through
In hydrogenation reactor.Hydrogenation reactor hydroconversion condition be 211 DEG C of reaction temperature, reaction pressure 3.2MPa, MAL quality
Air speed:0.7h-1.Jing after gas-liquid separator, vapor phase hydrogen is together with the fresh hydrogen being continuously replenished for material after reactor reaction
It is fed again in hydrogenation reactor, liquid phase obtains methallyl alcohol and unreacted metering system Jing after rectifying into rectifying column
Aldehyde, unreacted MAL enters hydrogenation reactor after separating.
The liquid product that analysis hydrogenation reactor outlet is collected:MAL conversion ratio 93.7%, methallyl alcohol choosing
Ze≤75.3%.Methallyl alcohol Chan product Chun Du≤99.6% that rectifying column rectifying is obtained, reaches top grade product grade.
Embodiment 14
The long period stability test of catalyst is carried out by the identical reaction process condition of embodiment 10 and 12.Reactor is filled
Fill out cylindrical catalyst, particle sizeLoadings 500g.Collect the liquid product of hydrogenation reactor outlet
It is analyzed, analysis result is shown in Table 2.
The stability experiment result of the catalyst for hydrogenation of table 2
Comparative example 2
In 450 milliliters of stainless steel high-pressure stirring reactors, the upper of 100.0 grams of MALs and 8.0 grams is separately added into
One kind of the catalyst of embodiment 1~4 is stated, desired reaction temperature, control reaction is risen in hydrogen exchange reactor after air 5 times
180 DEG C of temperature, reaction pressure 3.0MPa, 1000 revs/min of speed of agitator, reaction time 8h.Embodiment 1~4 and comparative example 1 are catalyzed
The reaction result of agent is shown in Table 3.
Metering system aldehyde hydrogenation reaction result on each catalyst in the tank reactor of table 3
Claims (5)
1. a kind of method that MAL selects Hydrogenation methallyl alcohol, MAL and hydrogen are continuously passed through to be equipped with and urge
In the fixed bed reactors of agent, continuous catalysis selective hydrogenation reaction, the product Jing gas of generation are carried out under certain reaction condition
Liquid separate and rectifying after obtain methallyl alcohol product and unreacted MAL, gas-liquid separation hydrogen out and rectifying
The equal circulating and recovering of unreacted MAL for obtaining afterwards;
Wherein, the catalyst includes the first component, the second component, third component and carrier;First component be Cu, Ag or
The metal or oxide of the mixture of Cu and Ag, the second component is at least one metal in Au, Ir, Ru and Pt or oxidation
Thing, third component is at least one metal or oxide in La, In, Co, Sn, Fe, Mn, and carrier is MgO, TiO2、Al2O3、
SiO2, activated carbon, diatomite, ZrO2, ZnO, HY molecular sieve, at least one in ZSM-5 molecular sieve;Wherein, the first constituent mass
Content is 0.1~33%, and the mass content of the second component is 0.1~5%, and the mass content of third component is 0.1~5%, is carried
The mass content of body is 57~99.7%;
The reaction condition is:Solvent-free, the mol ratio of hydrogen/aldehyde is 1~60:1, reaction temperature is 30~250 DEG C, reaction pressure
Power is 0.2~4.0MPa, and the mass space velocity of MAL is 0.1~5.0h-1。
2. the method that according to claim 1 MAL selects Hydrogenation methallyl alcohol, it is characterised in that adopt hydrogen
Gas is carried out selecting hydrogenation and removes heat, and reaction raw materials after fixed bed reactors, isolate by reactor outlet material Jing gas-liquid devices
Hydrogen recycle.
3. the method that according to claim 1 MAL selects Hydrogenation methallyl alcohol, it is characterised in that catalyst
Cylindrically shaped/cylindrical hollow, five tooth balls or cloverleaf pattern, 2.0~4.0mm of catalyst diameter, length is 2.0~
4.0mm。
4. the method that according to claim 1 MAL selects Hydrogenation methallyl alcohol, it is characterised in that catalyst
Using infusion process, sol-gal process, deposition-precipitation method;When being prepared using infusion process:Using the salting liquid containing the first component as
Single-steeping liquid, impregnation concentration is 0.05~1.0M, then to help containing two kinds or more in the second component and third component
Used as double-steeping liquid, impregnation concentration is 0.05~0.5M to the salting liquid of agent metal ion;Or with simultaneously by the first component, the
The salting liquid of one or two promoter metal ions impregnates as maceration extract in two components and third component, and afterwards carrier Jing does
Dry, roasting and reduction obtain required catalyst;When being prepared using sol-gal process:By the metal alkoxide or inorganic salts of carrier and respectively
The metal alkoxide or inorganic salts of active component is sufficiently mixed contact, gradually becomes gel by colloidal sol by hydrolytic condensation, through old
Change, be dried, roasting obtains catalyst precursor;When being prepared using deposition-precipitation method:Carrier is dissolved in into certain aqueous solution stirring,
Certain density metal salt solution and aqueous slkali are configured, according to certain order carrier aqueous solution stirring is added, and reached certain
PH, washing, filtering drying, roasting obtain catalyst precursor.
5. the method that according to claim 4 MAL selects Hydrogenation methallyl alcohol, it is characterised in that slaine
The one kind in polyethylene glycol, lauryl sodium sulfate, polyvinylpyrrolidone, neopelex is added in solution
Surfactant, surfactant concentration is 0~1.0M;The salt is sulfate, nitrate, the acetic acid of each metal active constituent
Salt, chloride:Catalyst needs dry, roasting and reduction, and baking temperature is 80~150 DEG C, and drying time is 8~24h;Roasting
Temperature is that roasting time is 4~12h at 250~600 DEG C;Reducing atmosphere is the mixed gas of hydrogen or hydrogen/nitrogen, is reduced
Pressure is 0.1~5MPa, temperature is 150~400 DEG C, reducing gas volume space velocity is 500~5000h-1, the recovery time be 3~
30h。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018157815A1 (en) * | 2017-03-01 | 2018-09-07 | 武汉凯迪工程技术研究总院有限公司 | Selective hydrogenation catalyst, method for preparing same, and catalytic evaluation method in generation of isobutyraldehyde |
CN110961110A (en) * | 2019-12-23 | 2020-04-07 | 上海华谊(集团)公司 | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine |
CN113019369A (en) * | 2021-03-23 | 2021-06-25 | 浙江皇马科技股份有限公司 | Copper-cobalt composite oxide supported catalyst and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1275441A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Alpah, Beta-unsaturated aldehyde selective hydrogenating reaction catalyst |
CN103755523A (en) * | 2013-12-02 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Preparation method for 2-methylallyl alcohol |
JP2015048349A (en) * | 2013-09-04 | 2015-03-16 | 国立大学法人東北大学 | Method for producing unsaturated alcohol |
CN104974016A (en) * | 2014-04-03 | 2015-10-14 | 长春工业大学 | Method for preparing cinnamyl alcohol through cinnamaldehyde hydrogenation |
EP2952252A1 (en) * | 2013-01-31 | 2015-12-09 | Osaka University | Selective hydrogenation catalyst, production method for selective hydrogenation catalyst, and selective hydrogenation method |
-
2016
- 2016-12-08 CN CN201611123365.9A patent/CN106631691A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1275441A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Alpah, Beta-unsaturated aldehyde selective hydrogenating reaction catalyst |
EP2952252A1 (en) * | 2013-01-31 | 2015-12-09 | Osaka University | Selective hydrogenation catalyst, production method for selective hydrogenation catalyst, and selective hydrogenation method |
JP2015048349A (en) * | 2013-09-04 | 2015-03-16 | 国立大学法人東北大学 | Method for producing unsaturated alcohol |
CN103755523A (en) * | 2013-12-02 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Preparation method for 2-methylallyl alcohol |
CN104974016A (en) * | 2014-04-03 | 2015-10-14 | 长春工业大学 | Method for preparing cinnamyl alcohol through cinnamaldehyde hydrogenation |
Non-Patent Citations (2)
Title |
---|
P. GALLEZOT & D. RICHARD: "Selective Hydrogenation of α,β-Unsaturated Aldehydes", 《CATAL.REV.-SCI.ENG.》 * |
杨树武等: "α,β不饱和醛中C=C和C=O键选择加氢的研究进展", 《分子催化》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018157815A1 (en) * | 2017-03-01 | 2018-09-07 | 武汉凯迪工程技术研究总院有限公司 | Selective hydrogenation catalyst, method for preparing same, and catalytic evaluation method in generation of isobutyraldehyde |
CN110961110A (en) * | 2019-12-23 | 2020-04-07 | 上海华谊(集团)公司 | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine |
CN110961110B (en) * | 2019-12-23 | 2022-11-08 | 上海华谊(集团)公司 | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination |
CN113019369A (en) * | 2021-03-23 | 2021-06-25 | 浙江皇马科技股份有限公司 | Copper-cobalt composite oxide supported catalyst and preparation method and application thereof |
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