CN103755523A - Preparation method for 2-methylallyl alcohol - Google Patents
Preparation method for 2-methylallyl alcohol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/14—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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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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Abstract
The invention provides a preparation method for 2-methylallyl alcohol. The preparation method for 2-methylallyl alcohol comprises the following steps: oxidizing isobutene into 2-methylacrolein in the presence of a catalyst A, vapour and air; reducing 2-methylacrolein into 2-methylallyl alcohol in the presence of a catalyst B and hydrogen. Because of using isobutene as a starting material, selectively oxidizing isobutene into methylacrolein by a metallic oxide, and then directly performing a hydrogenation reaction to produce 2-methylallyl alcohol, the method is high in yield, low in cost, low in energy consumption, and environment-friendly and clean.
Description
Technical field
The environment-friendly preparation method thereof that the present invention relates to a kind of 2-methallyl alcohol, belongs to field of chemical technology.
Background technology
2-methallyl alcohol (having another name called metallyl alcohol, isobutene alcohol or methallyl alcohol), is a kind of unsaturated alcohol, and colourless liquid, has irritating smell.It,, as a kind of very important organic intermediate, can be used as polymer monomer, resin and spices, also can make initiator, synthetic corresponding methacrylic acid and corresponding ester.Its most important purposes is synthesizing methyl allyl polyethenoxy ether.Methacrylic Soxylat A 25-7 be synthetic the 4th generation polycarboxylic acid series water reducing agent important monomer, it has decisive action for the efficient performance such as polycarboxylate water-reducer low-dosage, high diminishing, low slump.The application of methacrylic Soxylat A 25-7 can make the mobility of concrete mix and mobile retentivity is good, loss of slump is low, effect enhancing potentiality are large, shrinking percentage is low, thereby the purposes that makes polycarboxylate water-reducer is more extensive, adaptability is stronger, can be applicable to the important fields such as water conservancy, nuclear power engineering.12 planning ends, the concrete admixture field only demand of methacrylic Soxylat A 25-7 will reach 23.06 ten thousand tons, and 2-methallyl alcohol annual requirement is 1.0 ten thousand tons when the time comes, and market outlook are wide.In addition, 2-methallyl alcohol can also synthesize and contain allylic ester with other organic acid, therefore 2-methallyl alcohol has important application in the fields such as initiator, polymerization single polymerization monomer and tensio-active agent of the large monomer of concrete admixture polyethers, the research of its preparation method has larger economic benefit and social benefit.
Take 2-methallyl chloride as starting raw material, and adopting alkaline water solution to produce 2-methallyl alcohol is the industrial method of developing the earliest.
Patent US2072015, US2323781, US2313767 and JP2009107949 have mainly carried out Improvement and perfection around direct hydrolysis method.Yet, due to the activity of methylallyl chloride a little less than, while being conventionally hydrolyzed, need to add highly basic and organic solvent, and reaction must could react under higher temperature of reaction and pressure, severe reaction conditions, yield are lower, organic solvent is difficult to recovery; In addition, the growing amount of by product ether is also larger, and industry is purified comparatively difficult.Wherein, patent US2313767 has reported and has carried out at a lower temperature the method that vinyl carbinol is prepared in chlorallylene hydrolysis, adopts cylindrical reactor, and condenser low temperature recovery chlorallylene is set, but reaction efficiency is lower; Wherein, Japanese Patent JP2009107949 is used DMF facilitation of hydrolysis for fear of using heavy metal catalyst, and this reaction process will be introduced reluctant DMF solvent, and environment is caused to certain pollution.
Patent CN101759528 discloses the synthetic 2-methallyl alcohol of direct hydrolysis method of the methylallyl chloride that adopts Catalyzed by Polyethylene Glycol.Yet the alkali lye system circulation that the method is used is complicated, and the catalytic efficiency of polyoxyethylene glycol is lower, the yield of its single reaction is not high; In addition, production unit and energy consumption are larger, do not meet the green idea of current energy-saving and emission-reduction.
The main drawback of above-mentioned direct hydrolysis method is that the side reactions such as etherificate, esterification easily occur, and causes reaction efficiency not high, and requires to add the low concentration solution of highly basic, and the wastewater flow rate of discharge is large, and energy consumption is high.
Take 2-methallyl chloride as starting raw material, and adopting esterification catalysis two-step approach to produce 2-methallyl alcohol is current most widely used industrial method.
Patent CN103242139A discloses the technique of esterification catalysis two-step approach, adopted functional group's switch technology of organic synthesis, first synthesize 2-methallyl alcohol carboxylicesters, and then add the highly basic of lower concentration to be hydrolyzed, although increased synthesis step, but the functional group between compound is easy to conversion, and combined reaction efficiency is higher.Yet, although this scheme has improved reaction efficiency, need to add carboxylic acid sodium, highly basic and phase-transfer catalyst, cause reaction to produce a large amount of abraum salt, waste water.
The 2-methyl allyl aldehyde of take is starting raw material, and the method that adopts hydro-reduction reaction to produce 2-methallyl alcohol merits attention.US Patent No. 2779801, US2713074 and Japanese Patent JP-B56-36176 disclose and have adopted the reduction reaction that aluminium alcoholates is catalyzer, and temperature, pressure are all lower, and reaction conversion ratio and selectivity all can reach more than 90%, but Virahol demand is larger; US Patent No. 2767221 and US4731488 have reported take the gas phase hydrogen transfer reactions that polynary double oxide MgXYO that MgO is main body is catalyzer, the selectivity of acrolein conversion rate and vinyl carbinol reaches respectively 90% and 92%, but temperature of reaction is higher, catalyzer preparation needs high-temperature calcination; Domestic patent CN102167657 has also reported that take the catalytic hydrogenation reducing process that 2-methyl allyl aldehyde is starting raw material prepares 2-methallyl alcohol, but the required starting raw material 2-of this scheme methyl allyl aldehyde is unstable, is difficult to preserve and long-time transportation.
In sum, the traditional technology (direct hydrolysis method and esterification catalysis two-step approach) that the 2-methallyl chloride of take is prepared 2-methallyl alcohol as starting raw material generally exists highly basic, water or consumption of organic solvent larger, and be difficult to reclaim, this has also caused, and production cost is high, energy consumption is high, Industrial " three Waste " discharges the deficiencies such as more; The technique that the 2-methyl allyl aldehyde of take is the synthetic unsaturated alcohol of starting raw material has represented synthesis technique of new generation, yet need to add powerful catalyst and operational path research.
Summary of the invention
Goal of the invention: the object of the present invention is to provide that a kind of productive rate is high, cost is low, energy consumption is little, the environment-friendly preparation method thereof of the 2-methallyl alcohol of environment-protecting clean.
Technical scheme: the preparation method of a kind of 2-methallyl alcohol provided by the invention, comprises the following steps:
(1) under catalyst A, water vapour and air exist, iso-butylene is oxidized to 2-methyl allyl aldehyde;
(2) under catalyst B, hydrogen exist, 2-methacrylic aldehyde is reduced to 2-methallyl alcohol.
Its synthetic route is:
In step (1), the existence of water vapour atmosphere is very crucial to oxidizing reaction, and the volume ratio of described iso-butylene, water vapor and air is (4:4:92)～(8:8:84).
In step (1), oxidizing reaction temperature is 320～380 ℃, and oxidizing reaction air speed is 3000～6000h
-1.
In step (1), described catalyst A is Mo-Bi system complex oxide, and its structural formula can be expressed as: Mo
a-Bi
b-M
iI c-M
iII d-M
i e-X
f-O
g;
Wherein,
M
iIbe selected from Ni
2+, Co
2+, Mg
2+, Mn
2+, Cu
2+and Pb
2+in 1 to 3 kind;
M
iIIbe selected from Fe
3+, Cr
3+, Al
3+in 1 to 3 kind;
M
ibe selected from K
+, Na
+, Cs
+, Tl
+deng 1 in alkalimetal ion to 3 kinds;
X is P or B;
Wherein, a, b, c, d, e, f, g represent respectively the atomic ratio of every kind of element, a=12+ (1.6～4.0), and b=0.1～0.8, c=5～8, d=1.0～2.8, e=0～0.4, f=0～0.4, g is the numerical value that meets other element oxidation state;
The preparation method of catalyst A can adopt art methods, is specially: by the nitrate of ammonium molybdate and respective element ultrasonic 10～30min in water solution system, after fully mixing, co-precipitation obtains (referring to petrochemical complex, 2008,37,1133 or patent CN101088608A).
In step (2), the existence of liquid water is very crucial to reduction reaction, and the volume ratio of described 2-methyl allyl aldehyde and water is 0.8～1.2.
In step (2), reduction reaction temperature is 60～90 ℃, reduction reaction system pressure 0.4～1.0MPa, reduction reaction air speed 3～6h
-1.
In step (2), the structural formula of described catalyst B is M-ReOx/SiO
2-n;
Wherein,
M is selected from 1 to 2 kind in Ir, Rh, Pd, Ru and Pt; Preferably M is selected from one or both in Ir and Rh;
N represents Re/M value, n=0.8～1.2; The oxidation state of x representative element Re.
The preparation method of catalyst B can adopt art methods, referring to: Chem.Commun., 2013,49,7034; Appl.Catal., B, 2011,105,117.
Beneficial effect: the preparation method of a kind of 2-methallyl alcohol provided by the invention, take iso-butylene as starting raw material, by metal oxide selective oxidation, it is methyl allyl aldehyde, then directly there is hydrogenation reaction and produce the method for 2-methallyl alcohol, catalytic reaction efficiency is high, selectivity good, and technique is succinct, it is low to lower consumption, environmental friendliness, be easy to realize large-scale industrialization and produce.
Particularly, the present invention, with respect to prior art, has following outstanding advantage:
(1) the inventive method adopts that to take petrochemical complex C4 main fraction-iso-butylene be industrial raw material, directly by continuous redox reaction, prepare 2-methallyl alcohol, take with tradition 2-methallyl chloride as raw material carry out the synthetic target product of esterification catalysis two-step approach or direct hydrolysis method compare there is " Atom economy ", environmentally friendly, reaction is clean, without advantages such as " three industrial wastes " discharges.
(2) the catalyzer long service life that the inventive method is used, can continuous catalytic reaction in fixed-bed reactor more than 2000 hours and reaction yield without obvious reduction, greatly reduced cost, be easy to large-scale industrialization production.
(3) the inventive method is used catalyst efficiency is high, reaction preference is high, and the sufficient material of unreacted can circulating reaction, and product aftertreatment is simple, only needs simple rectifying to get final product to obtain more than 98% sterling.
(4) the inventive method new technology, succinct, equipment only needs the fixed-bed reactor of two series connection and corollary system just can realize, and cost of investment is low.
Accompanying drawing explanation
Fig. 1 is the hydrogen spectrogram of 2-methallyl alcohol.
Fig. 2 is the mass spectrum of 2-methallyl alcohol.
Fig. 3 is the process flow diagram that 2-methallyl alcohol is produced in a kind of serialization.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment, processing condition and result thereof be only for the present invention is described, and should also can not limit the present invention described in detail in claims.
The raw material iso-butylene that the present invention uses is industrial raw material, and iso-butylene purity should be more than 98.0%.
Embodiment 1
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
(1) under 25 ℃ of conditions of room temperature, by iso-butylene: the volume ratio charging of water vapour: air=6:6:88, charging air speed 4000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 360 ℃, the sampling of reactor thief hole, gas chromatographic detection, when iso-butylene≤0.1%, 2-methyl allyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methyl allyl aldehyde enters next step reaction unit;
(2) plant hydrogen first purges the fixed-bed reactor that are filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the aqueous solution of charging 2-methyl allyl aldehyde then, the volume ratio of controlling methacrolein and water is 1.2, is filled with plant hydrogen to H in reactor
2pressure keeps 0.8MPa, keeps air speed 4h
-180 ℃ of temperature of reaction, gas chromatographic detection, 2-methyl allyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 stage number are housed and purifies, and is slowly warming up to 150 ℃, keeps reflux ratio 1.5,100～120 ℃ of selections, the content of 2-methallyl alcohol can reach 99%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 89%, selection rate is 93%.
Product characterizes, and hydrogen spectrum is shown in Fig. 1, and gas-chromatography is shown in Fig. 2.
1H?NMR(CDCl
3,25℃,TMS),δ=1.74(s,3H,-CH
3),1.86(s,1H,-OH),4.02(s,2H,-CH2-),4.85(s,1H,),4.96(s,1H,)；IR(KBr):3093,2729,1662,1293,1179,949,820,660cm
-1。
EI-MS(75eV):m/z(%)80(26),65(14,[M-CH
3]
+),63(80,[M-OH]
+),56(96),41(100)。
Embodiment 2
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
1, under 25 ℃ of conditions of room temperature, by iso-butylene: the volume ratio charging of water vapour: air=8:8:84, charging air speed 3000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 380 ℃, the sampling of reactor thief hole, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methyl allyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methyl allyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor that are filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the aqueous solution of charging 2-methyl allyl aldehyde then, the volume ratio of controlling methacrolein and water is 0.8, is filled with plant hydrogen to H in reactor
2pressure keeps 1.0MPa, keeps air speed 6h
-190 ℃ of temperature of reaction, gas chromatographic detection, 2-methyl allyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 stage number are housed and purifies, and is slowly warming up to 150 ℃, keeps reflux ratio 1.5,100～120 ℃ of selections, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 88%, selection rate is 92%.
Product structure characterization data is close with embodiment 1.
Embodiment 3
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
1, under 25 ℃ of conditions of room temperature, by iso-butylene: the volume ratio charging of water vapour: air=4:4:92, charging air speed 6000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 340 ℃, the sampling of reactor thief hole, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methyl allyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methyl allyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor that are filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the aqueous solution of charging 2-methyl allyl aldehyde then, the volume ratio of controlling methacrolein and water is 1.0, is filled with plant hydrogen to H in reactor
2pressure keeps 0.4MPa, keeps air speed 6h
-170 ℃ of temperature of reaction, gas chromatographic detection, 2-methyl allyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 stage number are housed and purifies, and is slowly warming up to 150 ℃, keeps reflux ratio 1.5,100～120 ℃ of selections, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 90%, selection rate is 94%.
Product structure characterization data is close with embodiment 1.
Embodiment 4
The preparation method of 2-methallyl alcohol, is shown in Fig. 3, comprises the following steps:
1, under 25 ℃ of conditions of room temperature, by iso-butylene: the volume ratio charging of water vapour: air=5:5:90, charging air speed 5000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
13.6bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 350 ℃, the sampling of reactor thief hole, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methyl allyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methyl allyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor that are filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the aqueous solution of charging 2-methyl allyl aldehyde then, the volume ratio of controlling methacrolein and water is 1.1, is filled with plant hydrogen to H in reactor
2pressure keeps 0.5MPa, keeps air speed 5h
-180 ℃ of temperature of reaction, gas chromatographic detection, 2-methyl allyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 stage number are housed and purifies, and is slowly warming up to 150 ℃, keeps reflux ratio 1.5,100～120 ℃ of selections, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 89%, selection rate is 93%.
Product structure characterization data is close with embodiment 1.
Embodiment 5-10
Concrete steps, with embodiment 1, change the conditions such as input material volume ratio, air speed, temperature of reaction, and other conditions are identical with embodiment 1, and concrete outcome is in Table 1.
The impacts of condition on reaction yield such as table 1 input material volume ratio, air speed, temperature of reaction
Each product structure characterization data is close with embodiment 1.
Comparative example 1
With the continuous reaction apparatus shown in Fig. 3, proceed as follows process.
1, under 25 ℃ of conditions of room temperature, by the volume ratio charging of iso-butylene: air=8:92, charging air speed 5000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
12bi
0.6co
6fe
1.8cs
0.2b
0.2o
gtemperature of reaction is 360 ℃, the sampling of reactor thief hole, chromatography of gases detects, 2-methyl allyl aldehyde≤70.0%, reduces air speed or extends the reaction times, and the content of 2-methyl allyl aldehyde cannot promote, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methyl allyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor that are filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the aqueous solution of charging 2-methyl allyl aldehyde then, the volume ratio of controlling methacrolein and water is 1.0, is filled with plant hydrogen to H in reactor
2pressure keeps 0.8MPa, keeps air speed 5h
-180 ℃ of temperature of reaction, gas chromatographic detection, 2-methyl allyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 stage number are housed and purifies, and is slowly warming up to 150 ℃, keeps reflux ratio 1.5,100～120 ℃ of selections, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 68%, selection rate is 82%.
Product structure characterization data is the same close.
From this comparative example: be filled with water vapour in reactions steps 1 very crucial for improving the efficiency of oxidizing reaction and the selectivity of 2-methyl allyl aldehyde.
Comparative example 2
1, under 25 ℃ of conditions of room temperature, by iso-butylene: the volume ratio charging of water vapour: air=8:8:84, charging air speed 5000h
-1, the catalyst A molecular formula of fixed-bed reactor filling is: Mo
12bi
0.6co
6fe
1.8cs
0.2b
0.2o
g, temperature of reaction is 360 ℃, the sampling of reactor thief hole, chromatography of gases detects, and when iso-butylene≤0.1%, 2-methyl allyl aldehyde>=98.0%, shows to react completely, discharging enters condenser, gas-liquid separator successively, and the aqueous solution of isolated 2-methyl allyl aldehyde enters next step reaction unit.
2, plant hydrogen first purges the fixed-bed reactor that are filled with catalyst B, catalyst B molecular formula: Ir-ReOx/SiO
2-1, the aqueous solution of charging 2-methyl allyl aldehyde then, the volume ratio of controlling methacrolein and water is 1.0, is introduced into solution separating device, gets the organic layer charging of upper strata 2-methyl allyl aldehyde, is filled with plant hydrogen to H in reactor
2pressure keeps 0.8MPa, keeps air speed 5h
-180 ℃ of temperature of reaction, gas chromatographic detection, 2-methyl allyl aldehyde≤0.1%, 2-methallyl alcohol>=98.0%, show to react completely, material enters condenser, gas-liquid separator, isolated hydrogen circulates, liquid material is pumped to the rectifying tower that 16 stage number are housed and purifies, and is slowly warming up to 150 ℃, keeps reflux ratio 1.5,100～120 ℃ of selections, the content of 2-methallyl alcohol can reach 98%, comprehensively accounts, and the yield of two-step reaction 2-methallyl alcohol is 70%, selection rate is 92%.
Product structure characterization data is the same close.
From this comparative example: the water in reactions steps 2 in material is very crucial to the efficiency of reduction reaction.
Claims (7)
1. a preparation method for 2-methallyl alcohol, is characterized in that: comprise the following steps:
(1) under catalyst A, water vapour and air exist, iso-butylene is oxidized to 2-methyl allyl aldehyde;
(2) under catalyst B, hydrogen exist, 2-methacrylic aldehyde is reduced to 2-methallyl alcohol.
2. the preparation method of a kind of 2-methallyl alcohol according to claim 1, is characterized in that: in step (1), the volume ratio of iso-butylene, water vapor and air is (4:4:92)～(8:8:84).
3. the preparation method of a kind of 2-methallyl alcohol according to claim 1, is characterized in that: in step (1), oxidizing reaction temperature is 320～380 ℃, and oxidizing reaction air speed is 3000～6000h
-1.
4. the preparation method of a kind of 2-methallyl alcohol according to claim 1, is characterized in that: in step (1), the structural formula of catalyst A is: Mo
a-Bi
b-M
iI c-M
iII d-M
i e-X
f-O
g;
Wherein,
M
iIbe selected from Ni
2+, Co
2+, Mg
2+, Mn
2+, Cu
2+and Pb
2+in 1 to 3 kind;
M
iIIbe selected from Fe
3+, Cr
3+, Al
3+in 1 to 3 kind;
M
ibe selected from K
+, Na
+, Cs
+, Tl
+deng 1 in alkalimetal ion to 3 kinds;
X is P or B;
Wherein, a=12+ (1.6～4.0), b=0.1～0.8, c=5～8, d=1.0～2.8, e=0～0.4, f=0～0.4, g is the numerical value that meets other element oxidation state.
5. the preparation method of a kind of 2-methallyl alcohol according to claim 1, is characterized in that: in step (2), the volume ratio of 2-methyl allyl aldehyde and water is 0.8～1.2.
6. the preparation method of a kind of 2-methallyl alcohol according to claim 1, is characterized in that: in step (2), reduction reaction temperature is 60～90 ℃ reduction reaction system pressure 0.4～1.0MPa, reduction reaction air speed 3～6h
-1.
7. the preparation method of a kind of 2-methallyl alcohol according to claim 1, is characterized in that: in step (2), the structural formula of described catalyst B is M-ReOx/SiO
2-n;
Wherein,
M is selected from 1 to 2 kind in Ir, Rh, Pd, Ru and Pt;
N represents Re/M value, n=0.8～1.2; The oxidation state of x representative element Re.
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Cited By (8)
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|---|---|---|---|---|
| CN106631691A (en) * | 2016-12-08 | 2017-05-10 | 上海华谊（集团）公司 | Method for preparing methallyl alcohol through acrylaldehyde selective hydrogenization |
| CN107056566A (en) * | 2016-12-08 | 2017-08-18 | 上海华谊（集团）公司 | The method that α, β unsaturated aldehyde select Hydrogenation unsaturated alcohol |
| CN107266290A (en) * | 2017-07-20 | 2017-10-20 | 山东易达利化工有限公司 | A kind of method of methyl methacrylate coproducing methyl allyl alcohol |
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| CN108187746A (en) * | 2017-12-25 | 2018-06-22 | 苏州大学 | Three silicon amine rare earth metal complexs are in catalysis aldehyde and the application in pi-allyl acid reaction |
| CN109942370A (en) * | 2019-04-03 | 2019-06-28 | 山东理工大学 | The technique of green high-efficient synthesizing methyl allyl alcohol |
| CN111992248A (en) * | 2019-11-15 | 2020-11-27 | 北京水木滨华科技有限公司 | Catalyst for oxidation esterification of isobutene, preparation method and application thereof |
| CN113694860A (en) * | 2021-08-25 | 2021-11-26 | 宁波昊德化学工业股份有限公司 | Process and equipment for producing methallyl alcohol |
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| CN106631691A (en) * | 2016-12-08 | 2017-05-10 | 上海华谊（集团）公司 | Method for preparing methallyl alcohol through acrylaldehyde selective hydrogenization |
| CN107056566A (en) * | 2016-12-08 | 2017-08-18 | 上海华谊（集团）公司 | The method that α, β unsaturated aldehyde select Hydrogenation unsaturated alcohol |
| CN107365245A (en) * | 2017-07-10 | 2017-11-21 | 中国化学赛鼎宁波工程有限公司 | A kind of methallyl alcohol production system and method |
| CN107266290A (en) * | 2017-07-20 | 2017-10-20 | 山东易达利化工有限公司 | A kind of method of methyl methacrylate coproducing methyl allyl alcohol |
| CN108187746A (en) * | 2017-12-25 | 2018-06-22 | 苏州大学 | Three silicon amine rare earth metal complexs are in catalysis aldehyde and the application in pi-allyl acid reaction |
| CN108187746B (en) * | 2017-12-25 | 2020-08-14 | 苏州大学 | Application of trisilamide rare earth metal complex in catalyzing reaction of aldehyde and allyl boric acid |
| CN109942370A (en) * | 2019-04-03 | 2019-06-28 | 山东理工大学 | The technique of green high-efficient synthesizing methyl allyl alcohol |
| CN109942370B (en) * | 2019-04-03 | 2022-03-25 | 山东理工大学 | Green and efficient methallyl alcohol synthesis process |
| CN111992248A (en) * | 2019-11-15 | 2020-11-27 | 北京水木滨华科技有限公司 | Catalyst for oxidation esterification of isobutene, preparation method and application thereof |
| CN111992248B (en) * | 2019-11-15 | 2021-07-23 | 北京水木滨华科技有限公司 | Catalyst for oxidation esterification of isobutene, preparation method and application thereof |
| CN113694860A (en) * | 2021-08-25 | 2021-11-26 | 宁波昊德化学工业股份有限公司 | Process and equipment for producing methallyl alcohol |
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