CN102260148B - Method for synthesizing mixed aldehyde by synthetic gas - Google Patents
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Abstract
The invention discloses a method for synthesizing mixed aldehyde by synthetic gas. The method comprises the following step of: reacting CO and H2 in the presence of a catalyst to form the mixed aldehyde, wherein the reaction is carried out under the acid or neutral condition; the structural formula of the aldehyde is shown as a formula (I), and in the formula, R1 is alkyl with 1 to 30 carbon atoms; and the catalyst is a mixture of transition metal nanoparticles and polyatomic alcohol, or a mixture of transition metal nanoparticles, polyatomic alcohol and water. Reaction materials are rich in sources and low in prices; the aldehyde selectivity is over 40 percent, and the method for synthesizing the mixed aldehyde is a green novel synthesis route and has wide application prospect.
Description
Technical field
The present invention relates to a kind of synthetic method of aldehyde, particularly a kind of method of directly being synthesized mixed aldehyde by synthetic gas.
Background technology
Aldehyde, i.e. acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal etc.Aldehyde is the fine chemical product that is widely used.At present, the preparation of aldehyde mainly obtains via hydroformylation, and namely alkene and synthesis gas reaction prepare aldehyde.But alkene is expensive, is that economic worth is arranged very much if can develop from the synthetic gas one step preparation aldehyde of cheapness.
The synthetic gas wide material sources can obtain from coal, Sweet natural gas and biomass.Prepare fuel by synthetic gas, be expected to the fuels and chemicals problem in short supply of bringing solving the oil exhaustion.In today of petroleum resources worsening shortages, from CO and H
2(synthetic gas) sets out synthetic via Fischer-Tropsch, and the synthetic a series of processes that wait reaction preparation fuels and chemicals of methyl alcohol more and more are taken seriously, also heavy industrialization.Except from synthetic gas is produced fuel, the chemical of the high added value that selectivity generates is the very interested research contents of people
This shows, the method for preparing aldehyde from one step of synthetic gas has the advantage that raw material sources extensively are easy to get, and meets the requirement of society Sustainable development, is the new synthesis route of a green, economy.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of new mixed aldehyde.
The synthetic method of mixed aldehyde provided by the invention comprises the steps: under the condition of acidic conditions and catalyzer existence CO and H
2React and namely get described mixed aldehyde, the structural formula of described mixed aldehyde is all suc as formula shown in (I), wherein, and R
1Alkyl for C1-C30; Described catalyzer is the mixture of transition metal nanoparticles, polyvalent alcohol and water; In described mixture, described polyvalent alcohol is (1-9) with the volume parts ratio of water: (1-9); The pH value of described acidic conditions is 1-6;
In above-mentioned synthetic method, described polyvalent alcohol is recyclable to be reused.
In above-mentioned synthetic method, described polyvalent alcohol is preferably dibasic alcohol, and described dibasic alcohol can be ethylene glycol, 1, ammediol, BDO, 1,2-butyleneglycol, 1,3-butyleneglycol, 2,4-butyleneglycol, 1,2-PD, 1,5-PD, 1,2 pentanediols, 1, at least a in 3 pentanediols, Isosorbide-5-Nitrae pentanediol and 1,6 hexylene glycol.
In above-mentioned synthetic method, described transition metal nanoparticles can be nanoparticle at least a in Fe, Co and Ru; The particle diameter of described transition metal nanoparticles can be 1nm-1000nm, specifically can be 1nm-3nm or 7nm-9nm.
In above-mentioned synthetic method, the temperature of described reaction can be 80 ℃-220 ℃, specifically can be 130 ℃; The time of described reaction can be 1 hour-100 hours, specifically can be 12 hours.
In above-mentioned synthetic method, described CO and H
2Total pressure can be 0.1MPa-10MPa, specifically can be 4.5MPa; Described H
2Can be (0.5-3) with the molfraction ratio of CO: 1, specifically can be 2: 1.
In above-mentioned synthetic method, in the mixture of described transition metal nanoparticles, polyvalent alcohol and water, densitometer with the transition metal ion in the corresponding transition metal salt of described transition metal nanoparticles, the volumetric molar concentration of described transition metal nanoparticles can be 0.005mol/L-10mol/L, specifically can be 0.00925mol/L or 0.05mol/L; Described transition metal nanoparticles can be (0.001-20) with the molfraction ratio of described polyvalent alcohol: 1, specifically can be 0.001: 1,0.0017: 1,0.003: 1,0.0052: 1 or 0.007: 1; Described polyvalent alcohol can be 1: 1 with the volume parts ratio of water, 1: 9,3: 7 or 7: 3; Described transition metal salt is at least a in Fe salt, Co salt and Ru salt.
In above-mentioned synthetic method, described metal nanoparticle can prepare according to the method that comprises the steps: use H
2, NaBH
4Or KBH
4Transition metal salt is reduced namely get described metal nanoparticle; Described transition metal salt is at least a in Fe salt, Co salt and Ru salt.
In above-mentioned synthetic method, described Fe salt can be selected from following salt at least a: FeCl
24H
2O, FeCl
36H
2O, FeSO
47H
2O, FeCl
3, Fe (NO
3)
3And Fe
2(SO
4)
39H
2At least a in O; Described Co salt can be selected from following salt at least a: CoCl
26H
2O, CoC
2O
42H
2O, CoSO
47H
2O, Co (NO
3)
36H
2O and CoSO
47H
2O； Described Ru salt can be selected from following salt at least a: RuCl
3NH
2O and RuCl
3
In above-mentioned synthetic method, can add hydroformylation catalyst in described reaction, can improve the selectivity of aldehyde, described hydroformylation catalyst can be Rh-TPPTS, HCo (CO)
3, HCo (CO)
3And HRh (CO)
4In at least a.
In above-mentioned synthetic method, contain acetaldehyde in described mixed aldehyde; The pH value of described acidic conditions can be 2.
The synthetic method of mixed aldehyde provided by the invention has the following advantages:
1. prepare mixed aldehyde by synthetic gas.
2. catalyzer is that catalyst with metal nanoparticles is dispersed in liquid phase reaction medium.
3. the pH value of reaction system can be regulated.
4. the senior aldehyde that comprises acetaldehyde and Geng Gao carbon number in mixed aldehyde.
5. the selectivity of aldehyde can be regulated by the kind and the content that change polyvalent alcohol in liquid phase reaction medium.
6. the selectivity of aldehyde reaches more than 40%.
Description of drawings
Fig. 1 is TEM photo and the size distribution of the Ru nanoparticle in embodiment 1, and wherein, in Fig. 1, (a) is the TEM photo of Ru nanoparticle, and in Fig. 1, (b) is the size distribution of Ru nanoparticle.
Fig. 2 is TEM photo and the XRD characterization result of the Fe nanoparticle in embodiment 5, and wherein, in Fig. 2, (a) is the TEM photo of Fe nanoparticle, and in Fig. 2, (b) is the XRD characterization result of Fe nanoparticle.
Fig. 3 is TEM photo and the XRD characterization result of the Co nanoparticle in embodiment 6, and wherein, in Fig. 3, (a) is the TEM photo of Co nanoparticle, and in Fig. 3, (b) is the XRD characterization result of Co nanoparticle.
Fig. 4 is embodiment 3 portion of product color atlass; In Fig. 4, (a) is the color atlas of 0-14min; The color atlas of (b) 0-2min in Fig. 4.
Embodiment
The experimental technique that uses in following embodiment is ordinary method if no special instructions.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
The measuring method of product in following each embodiment: gaseous product adopts the gas-chromatography quantitative assay; Product liquid adopts gas-chromatography quantitative assay (dodecane is as interior mark) after extracting with hexanaphthene; Concrete test condition: gas-chromatography (GC) product analysis condition: post case: 60 ℃ of initial temperatures, residence time 4min, 10 ℃/min of velocity slope, 150 ℃ of outlet temperatures (detected gas), residence time 4min; 220 ℃ (tracer liquid), residence time 4min; Injection port: 50 ℃, gas type N
2, fid detector: 250 ℃, make-up gas N
2
Synthesizing of embodiment 1, aldehyde
(1) hydrogen reducing prepares precious metal Ru nanoparticle: weighing RuCl
33H
2O 94.6mg (0.37 * 10
-3Mol), PVP K30 1.013g (9.12 * 10
-3Mol) be dissolved in 40.0ml water, be transferred in still.Be filled with 2.0MPaH in still
2, 150 ℃ of lower reduction reactions 2 hours, stirring velocity was 800r/min.After kettle is cooling, solution is taken out, namely get the concentration 9.25 * 10 of 40ml Ru
-3Mol/L, PVP/Ru=25: 1 Ru nanoparticle (particle diameter is 1nm-3nm, as shown in Fig. 1 (a) and Fig. 1 (b)) solution.Steam by outstanding the water of removing in solution, then pour the mixed solution of 4.0ml ethylene glycol and 36.0ml water into, the fully dissolving that stirs obtains aqueous glycol solution, and in this aqueous solution, the concentration of Ru nanoparticle is with RuCl
33H
2Ru in O
2+Concentration counts 9.25 * 10
-3Mol/L, the Ru nanoparticle is 0.0052: 1 with the molfraction ratio of ethylene glycol, and the volume parts ratio of ethylene glycol and water is 1: 9, and the pH value is 2.
(2) aldehyde is synthetic: then be filled with 3.0MPa H in above-mentioned system
2, 1.5MPa CO, H
2With the molfraction ratio of CO be 2: 1, under 130 ℃ the reaction 12 hours.Gaseous tension in the mensuration system, the decline total pressure of counting system, transformation frequency the results are shown in Table 1.Through chromatographic determination, product aldehyde is the aldehyde of C1-C30.
Synthesizing of embodiment 2, aldehyde
(1) hydrogen reducing prepares precious metal Ru nanoparticle: weighing RuCl
33H
2O 94.6mg (0.37 * 10
-3Mol), PVP K30 1.013g (9.12 * 10
-3Mol) be dissolved in 40.0ml water, be transferred in still.Be filled with 2.0MPaH in still
2, 150 ℃ of lower reduction reactions 2 hours, stirring velocity was 800r/min.After kettle is cooling, solution is taken out, namely get the concentration 9.25 * 10 of 40ml Ru
-3Mol/L, PVP/Ru=25: 1 Ru nanoparticle (particle diameter is 1nm-3nm) solution.Steam by outstanding the water of removing in solution, then pour the mixed solution of 12.0ml ethylene glycol and 28.0ml water into, the fully dissolving that stirs obtains aqueous glycol solution, and in this aqueous solution, the concentration of Ru nanoparticle is with RuCl
33H
2Ru in O
2+Concentration counts 9.25 * 10
-3Mol/L, the Ru nanoparticle is 0.0017: 1 with the molfraction ratio of ethylene glycol, and the volume parts ratio of ethylene glycol and water is 3: 7, and the pH value is 2.
(2) aldehyde is synthetic: then be filled with 3.0MPa H in above-mentioned system
2, 1.5MPa CO, H
2With the molfraction ratio of CO be 2: 1, under 130 ℃ the reaction 12 hours.Gaseous tension in the mensuration system, the decline total pressure of counting system, transformation frequency the results are shown in Table 1.Through chromatographic determination, product aldehyde is the aldehyde of C1-C30.
Synthesizing of embodiment 3, aldehyde
(1) hydrogen reducing prepares precious metal Ru nanoparticle: weighing RuCl
33H
2O 94.6mg (0.37 * 10
-3Mol), PVP K30 1.013g (9.12 * 10
-3Mol) be dissolved in 40.0ml water, be transferred in still.Be filled with 2.0MPaH in still
2, 150 ℃ of lower reduction reactions 2 hours, stirring velocity was 800r/min.After kettle is cooling, solution is taken out, namely get the concentration 9.25 * 10 of 40ml Ru
-3Mol/L, PVP/Ru=25: 1 Ru nanoparticle (particle diameter is 1nm-3nm) solution.Steam by outstanding the water of removing in solution, then pour the mixed solution of 20.0ml ethylene glycol and 20.0ml water into, the fully dissolving that stirs obtains aqueous glycol solution, and in this aqueous solution, the concentration of Ru nanoparticle is with RuCl
33H
2Ru in O
2+Concentration counts 9.25 * 10
-3Mol/L, the Ru nanoparticle is 0.001: 1 with the molfraction ratio of ethylene glycol, and the volume parts ratio of ethylene glycol and water is 1: 1, and the pH value is 2.
(2) aldehyde is synthetic: then be filled with 3.0MPa H in above-mentioned system
2, 1.5MPa CO, H
2With the molfraction ratio of CO be 2: 1, under 130 ℃ the reaction 12 hours.Gaseous tension in the mensuration system, the decline total pressure of counting system, transformation frequency the results are shown in Table 1.Wherein the aldehyde product is acetaldehyde, propionic aldehyde, butyraldehyde, valeral, and the higher serial senior aldehyde of carbon number.The portion of product color atlas is referring to Fig. 4.
Synthesizing of embodiment 4, aldehyde
(1) hydrogen reducing prepares precious metal Ru nanoparticle: weighing RuCl
33H
2O 94.6mg (0.37 * 10
-3Mol), PVP K30 1.013g (9.12 * 10
-3Mol) be dissolved in 40.0ml water, be transferred in still.Be filled with 2.0MPaH in still
2, 150 ℃ of lower reduction reactions 2 hours, stirring velocity was 800r/min.After kettle is cooling, solution is taken out, namely get the concentration 9.25 * 10 of 40ml Ru
-3Mol/L, PVP/Ru=25: 1 Ru nanoparticle (particle diameter is 1nm-3nm) solution.Steam by outstanding the water of removing in solution, then pour the mixed solution of 28.0ml ethylene glycol and 12.0ml water into, the fully dissolving that stirs obtains aqueous glycol solution, and in this aqueous solution, the concentration of Ru nanoparticle is with RuCl
33H
2Ru in O
2+Concentration counts 9.25 * 10
-3Mol/L, the Ru nanoparticle is 0.007: 1 with the molfraction ratio of ethylene glycol, and the volume parts ratio of ethylene glycol and water is 7: 3, and the pH value is 2.
(2) aldehyde is synthetic: then be filled with 3.0MPa H in above-mentioned system
2, 1.5MPa CO, H
2With the molfraction ratio of CO be 2: 1, under 130 ℃ the reaction 12 hours.Gaseous tension in the mensuration system, the decline total pressure of counting system, transformation frequency the results are shown in Table 1.Through chromatographic determination, product aldehyde is the aldehyde of C1-C30.
Synthesizing of embodiment 5, aldehyde
(1) preparation of catalyzer: with 400mgFeCl
24H
2O joins in the Erlenmeyer flask that volume is 60ml, then pours 10.0ml ethylene glycol into, and the fully dissolving that stirs obtains containing Fe
2+Concentration is the solution A of 0.20mol/L.With 500mgNaBH
4Add in the 50ml beaker, add 1.0ml deionized water and 4.0ml ethylene glycol, fully dissolving obtains solution B, under high degree of agitation again, pour solution B into solution A, sealing immediately, afterreaction finished in one minute, with magnet, Fe was inhaled at the bottom of bottle, when solvent is clarified, it is poured out, then use washed with de-ionized water three times, then remove moisture (removing solvent with magnetism separate method equally) with reaction with solvent wash, obtain the Fe nanoparticle; The Fe nanoparticle that obtains is dispersed in 40.0ml ethylene glycol, and (wherein, the amount of Fe nanoparticle is with FeCl namely to get catalyzer
24H
2Fe in O
2+Densitometer is 0.050mol/L), the Fe nanoparticle is 0.003: 1 with the molfraction ratio of ethylene glycol, the pH value is 7.The particle diameter of Fe nanoparticle of preparation is 7nm-9nm, the transmission electron microscope photo of Fe nanoparticle and XRD result as shown in Figure 2, the XRD result shows that the Fe nanometer particles before sintering presents unformed state, the iron catalyst after sintering is the iron of zeroth order.
(2) aldehyde is synthetic: pour the catalyzer of above-mentioned preparation into the 140ml autoclave, then be filled with 1.5MPaCO, 3.0MPa H
2(1atm=0.101325Mpa), H
2With the molfraction ratio of CO be 2: 1, under 130 ℃ the reaction 12 hours.Gaseous tension in the mensuration system, the decline total pressure of counting system (degree of the pressure representative reaction of decline), transformation frequency (amount (mol) of the amount of the CO of transformation frequency=conversion (mol)/catalyzer/reaction times (h)) the results are shown in Table 1.Through chromatographic determination, product aldehyde is the aldehyde of C1-C30.
Synthesizing of embodiment 6, aldehyde
(1) preparation of catalyzer: with 400mg FeCl
24H
2O joins in the Erlenmeyer flask that volume is 60ml, then pours 10.0ml ethylene glycol into, and the fully dissolving that stirs obtains containing Fe
2+Concentration is the solution A of 0.20mol/L.With 500mg NaBH
4Add in the 50ml beaker, add 1.0ml deionized water and 4.0ml ethylene glycol, fully dissolving obtains solution B, under high degree of agitation again, pour solution B into solution A, sealing immediately, afterreaction finished in one minute, with magnet, the Fe catalyzer was inhaled at the bottom of bottle, when solvent is clarified, it is poured out, then use washed with de-ionized water three times, then remove moisture (removing solvent with magnetism separate method equally) with reaction with solvent wash, obtain Fe nanometer particles (particle diameter is 7nm-9nm); The Fe nanometer particles that obtains is dispersed in 40.0ml ethylene glycol, namely gets catalyzer, wherein, the Fe nanoparticle is 0.0028: 1 with the molfraction ratio of ethylene glycol, and the pH value is 7.
(2) aldehyde is synthetic: pour together catalyzer and the 0.1g Rh-TPPTs of above-mentioned preparation into the 140ml autoclave, then be filled with 1.5MPa CO, 3.0MPa H
2, H
2With the molfraction ratio of CO be 2: 1, under 130 ℃ the reaction 12 hours.Gaseous tension in the mensuration system, the decline total pressure of counting system (degree of the pressure representative reaction of decline), transformation frequency (amount (mol) of the amount of the CO of transformation frequency=conversion (mol)/catalyzer/reaction times (h)) the results are shown in Table 1.Through chromatographic determination, product aldehyde is the aldehyde of C1-C30.
Table 1, the transformation frequency of different catalysts in the differential responses thing
Above result shows, the method can obtain aldehyde (ketone) from the synthetic gas highly selective under mild conditions.In the reaction of Ru catalyst, aldehyde product content higher (17wt%).The further hydrolysis of acetal product can also obtain aldehyde, so the theoretical selectivity of aldehyde reaches more than 40%.
Claims (9)
1. the synthetic method of a mixed aldehyde, comprise the steps: under the condition of acidic conditions and catalyzer existence CO and H
2React and namely get described mixed aldehyde, the structural formula of described mixed aldehyde all as shown in formula I, wherein, R
1Alkyl for C1-C30; Described catalyzer is the mixture of transition metal nanoparticles, polyvalent alcohol and water; In described mixture, described polyvalent alcohol is (1-9) with the volume parts ratio of water: (1-9); The pH of described acidic conditions is 1-6; Described polyvalent alcohol is ethylene glycol, 1,3-PD, BDO, 1,2-butyleneglycol, 1,3 butylene glycol, 1,2-PD, 1,5-PD, 1, and 2-pentanediol, 1, at least a in 3-pentanediol, Isosorbide-5-Nitrae-pentanediol and 1,6-hexylene glycol; The particle diameter of described transition metal nanoparticles is 1nm-1000nm;
2. method according to claim 1, it is characterized in that: described transition metal nanoparticles is nanoparticle at least a in Fe, Co and Ru.
3. method according to claim 1 and 2, it is characterized in that: the temperature of described reaction is 80 ℃-220 ℃; The time of described reaction is 1 hour-100 hours.
4. method according to claim 1 and 2, is characterized in that: described CO and H
2Total pressure be 0.1MPa-10MPa; Described H
2With the mol ratio of CO be (0.5-3): 1.
5. method according to claim 1, it is characterized in that: in the mixture of described transition metal nanoparticles, polyvalent alcohol and water, with the densitometer of the transition metal ion in the corresponding transition metal salt of described transition metal nanoparticles, the volumetric molar concentration of described transition metal nanoparticles is 0.005mol/L-10mol/L; Described transition metal nanoparticles is (0.001-20) with the molfraction ratio of described polyvalent alcohol: 1; Described transition metal salt is at least a in Fe salt, Co salt and Ru salt.
6. method according to claim 1 is characterized in that: described metal nanoparticle is according to the method preparation that comprises the steps: use H
2, NaBH
4Or KBH
4Transition metal salt is reduced namely get described metal nanoparticle; Described transition metal salt is at least a in Fe salt, Co salt and Ru salt.
7. according to claim 5 or 6 described methods, it is characterized in that: described Fe salt is selected from following salt at least a: FeCl
24H
2O, FeCl
36H
2O, FeSO
47H
2O, FeCl
3, Fe (NO
3)
3And Fe
2(SO
4)
39H
2At least a in O; Described Co salt is selected from following salt at least a: CoCl
26H
2O, CoC
2O
42H
2O, Co (NO
3)
36H
2O and CoSO
47H
2O； Described Ru salt is RuCl
3
8. method according to claim 1, it is characterized in that: add hydroformylation catalyst in described reaction, described hydroformylation catalyst is Rh-TPPTS, HCo (CO)
3And HRh (CO)
4In at least a.
9. method according to claim 1, is characterized in that: contain acetaldehyde in described mixed aldehyde; The pH value of described acidic conditions is 2.
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| Chao-xian Xiao，et al..Aqueous-Phase Fischer–Tropsch Synthesis with a Ruthenium Nanocluster Catalyst.《Angewandte Chemie international edition》.2007,第47卷746-749. * |
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