CN107866249A - For citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol - Google Patents
For citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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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
Abstract
For citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol：The XRD diffraction spectrograms of the molybdenum carbide catalyst are by 2 θ differences with one kind in following four groups of kind features：36~38 °, 41~43 °, 61~63 °, 73~75 °；34~35 °, 37~38 °, 39~40 °, 51~53 °, 61~63 °, 69~71 °, 72~73 °, 74~75 °, 75~76 °；36~39 °, 42~44 °, 62~65 °, 74~77 °；25~27 °, 34~35 °, 36~37 °, 37~39 °, 39~41 °, 51~53 °, 53~54 °, 61~63 °, 68~70 °, 71~73 °, 73.5~75 °, 75~77 °.
Description
Technical field
The present invention relates to the molybdenum carbide catalyst for citral Hydrogenation nerol and geraniol and its application.
Background technology
Citral (citral) is a kind of important α, beta-unsaturated aldehyde, has two kinds of geometric isomers：Geranial is (anti-
Formula, citral A) and neral (cis, citral B), contained citral is based on citral B in lemongrass oil.Its selectivity
Hydrogenation products unsaturated alcohol is nerol and geraniol (cis/trans -3,7- dimethyl -2,6- octadiene-l- alcohol) is two kinds valuable
Spices and medicine intermediate, be with a wide range of applications in industries such as essence, medicine (Li Qiugui, Liu Yingxin, Wang Guilin,
Deng progress [J] modern chemical industries of citrals selective hydrogenation synthesis nerol/spiceleaf alcohol catalyst, 2007 (S2):32-
36.), therefore nerol is synthesized to citral selective catalytic hydrogenation by Recent study person and geraniol reaction receives researcher
Extensive concern and probe into.
Carbonyl and double bond in lemon aldehyde structure be present, the chemical reaction such as addition, condensation, cyclisation and oxidation easily occurs.Lemon
In lemon aldehyde carbonyl can be reduced, addition and condensation reaction, lemonile, nerol (nerol) and geraniol can be synthesized
(geraniol), acetal and mercaptal, pseudo ionone and irisone, cyclocitral, β-damascone and irone
(irone), timberone and timber alcohol etc..The double bond property of can be chosen catalytic hydrogenation in citral, obtains dihydro lemongrass
Aldehyde, citronellal and citronellol (Qin Ting, Lv Qiqi, Li Xingyu, wait perfume synthesis progress [J] of using citral as raw material
Chemical Industry in Guangzhou, 2014 (20)).
Catalyst is relevant with metal surface activation C=C and C=O ability to the hydrogenation activity of citral, and catalyst is not to
The selectivity of saturated alcohols is relevant with the absorption mode of reactant molecule with catalyst.Therefore, to improve the yield of unsaturated alcohol
Ask catalyst that not only there is high activity, and tackle C=O there is high selectivity.Flores aurantii is synthesized for citral selective hydrogenation
The catalyst activity component of alcohol/geraniol can be divided into two major classes：One kind is base metal, such as Ni, Co；Your gold another kind of be
Category, such as Pd, Pt, Rh and Ru.Different active components, it is poor that the effect shown to lemon aldehyde carbonyl groups selective hydrogenation is present
It is different.
Non-precious metal catalyst active component for citral selective hydrogenation focuses mostly in metals such as Ni and Co.
Ikushima etc. loads Ni using molecular sieve MCM-41 and is hydrogenated with as catalyst citral, in subcritical CO2Middle lemon
Aldehyde is hydrogenated to nerol and geraniol, selectivity up to 99%.Gieck etc. has investigated MgCo6Ge6、MgCo4Ge6Deng catalyst pair
Citral Hydrogenation finds that such catalyst has very high selectivity (Gieck for nerol and the catalytic performance of geraniol
C,Schreyer M, T F,et al.Synthesis,Crystal Structure,and Catalytic
Properties of MgCo6Ge6[J].Chemistry,2006,12(7):1924–1930.；Gieck C,Schreyer M, T F,et al.Crystal structure and properties of MgCo4Ge6[J].2006.).In addition,
Mg2Sn also shows higher selectivity (Claus P, Raif F, Cavet S, et al.From to citral hydrogenation
molecule to material:Mg2Sn as hydrogenation catalyst[J].Catalysis
Communications,2006,7(9):618-622.)。
In recent years for lemon aldehyde carbonyl groups selective hydrocatalyst noble metal active composition be mainly Ru, Rh, Pt,
Ir, Os etc..Wherein, Os, Rh, Ir show very high selectivity to nerol and geraniol.Os/SiO2、Rh-Ge/A12O3、
Ir/SiO2、Ir/TiO2Deng catalyst to the selectivity of nerol and geraniol up to 100%；By contrast, Ru metallic catalysts
Selectivity slightly reduces, but activity is higher, such as Ru/A12O3、Ru/TiO2Citral conversion ratio is up to 100% on catalyst.Au/
Fe2O3Catalyst has high activity and selectivity under the conditions of relatively mild.
But there is the shortcomings that cost is high, stock number is few in noble metal catalyst, seek its substitute turns into trend.
The content of the invention
One of the technical problem to be solved in the present invention is the problem of conventional noble metal hydrogenation catalyst cost is high, there is provided is used
In citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol.
The second technical problem to be solved by the present invention is the preparation method of above-mentioned molybdenum carbide catalyst.
The third technical problem to be solved by the present invention is molybdenum carbide catalyst in citral Hydrogenation nerol and geraniol
Application in reaction as catalyst.
To solve one of above-mentioned technical problem, technical scheme is as follows：For citral Hydrogenation nerol and
The molybdenum carbide catalyst of geraniol：The XRD diffraction spectrograms of the molybdenum carbide catalyst have one kind in following four kinds of features：
(a) peak position：θ=36~38 ° of 1a peaks 2, θ=41~43 ° of 2a peaks 2, θ=61~63 ° of 3a peaks 2, θ=73 of 4a peaks 2
~75 °；
Peak intensity ratio：1a:2a=1~2:1,1a:3a=1.5~3:1,1a:4a=1.5~3:1；
(b) peak position：θ=34~35 ° of 1b peaks 2, θ=37~38 ° of 2b peaks 2, θ=39~40 ° of 3b peaks 2, θ=51 of 4b peaks 2
~53 °, θ=61~63 ° of 5b peaks 2, θ=69~71 ° of 6b peaks 2, θ=72~73 ° of 7b peaks 2, θ=74~75 ° of 8b peaks 2, the θ of 9b peaks 2
=75~76 °；
Peak intensity ratio：1b:2b=1~2:1,1b:3b=0.2~0.6:1,1b:4b=1.5~3:1,1b:5b=0.8~
1.5:1,1b:6b=1.5~3:1,1b:7b=3~7:1,1b:8b=1~3:1,1b:9b=1.5~3:1；
(c) peak position：θ=36~39 ° of 1c peaks 2, θ=42~44 ° of 2c peaks 2, θ=62~65 ° of 3c peaks 2, θ=74 of 4c peaks 2
~77 °；
Peak intensity ratio：1c:2c=1.5~2.5:1,1c:3c=2.5~3.5:1,1c:4c=3~4:1；
(d) peak position：θ=25 of 1d peaks 2~27o, θ=34 of 2d peaks 2~35o, θ=36 of 3d peaks 2~37o, θ=37 of 4d peaks 2
θ=39 of~39o, 5d peak 2~41o, θ=51 of 6d peaks 2~53o, θ=53 of 7d peaks 2~54o, θ=61 of 8d peaks 2~63o, the θ of 9d peaks 2
θ=71 of=68~70o, 10d peak 2~73o, θ=73.5 of 11d peaks 2~75o, θ=75 of 12d peaks 2~77o；
Peak intensity ratio：1d:2d=0.1~2:1,1d:3d=0.2~2:1,1d:4d=0.2~2.5:1,1d:5d=0.1
~1.5:1,1d:6d=0.5~2:1,1d:7d=0.5~2:1,1d:8d=0.1~2:1,1d:9d=0.5~2:1,1d:
10d=0.5~3:1,1d:11d=0.2~2:1,1d:12d=0.5~2:1.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The carbonization of one of above-mentioned technical problem
The preparation method of molybdenum catalyst, comprises the following steps：
(1) organic amine is added in the aqueous solution of molybdenum source and be well mixed, be that 0.5~6.5 (such as pH is specific with acid for adjusting pH
Can be：0.5,1,0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5,5,6.0 or 6.5), obtain containing flocky precipitate
Material I；
(2) the material I is carried out being thermally treated resulting in material II；
(3) material II progress separation of solid and liquid is obtained into solid material III；
(4) roasting obtains the catalyst in the atmosphere inert to molybdenum carbide.
In above-mentioned technical proposal, molybdenum atom concentration is preferably 0.001~1.0mol/L in the aqueous solution of step (1) molybdenum source,
Such as the concentration of molybdenum atom is specifically as follows：0.005,0.01,0.04,0.08,0.15,0.25,0.30,0.40,0.50,
0.60,0.70,0.80,0.9 or 1.0mol/L；The mol ratio of organic amine and molybdenum atom is preferably 30.0~4.0:1, for example, it is organic
The mol ratio of amine and molybdenum atom is concretely：30.0,25.0,20.0,18.0,16.0,14.0,12.0,10.0,8.0,6.0 or
4.0；Described organic amine more preferably refers to be selected from primary amine nitrogen, secondary amine nitrogen or tertiary amine containing carbonnitrogen bond and nitrogen-atoms in the molecule
Nitrogen.Carbon number in organic amine molecule is not particularly limited, such as, but not limited to C2~C10Organic amine, further it is non-limiting
It is exemplified as fatty amine, C6~C10Aromatic amine, hydramine, aliphatic cyclic amine etc..As more specifically non-limiting example, described amine
Can be aniline, 1,2- propane diamine, lauryl amine, 1,6- hexamethylene diamines, monoethanolamine, diethanol amine, triethanolamine, ethylenediamine, diethyl
Alkene triamine, triethylene tetramine, TEPA etc..
In above-mentioned technical proposal, the temperature of step (2) heat treatment is preferably 40~70 DEG C, and time preferably 4 of heat treatment~
24 hours.
In above-mentioned technical proposal, those skilled in the art will know that before the roasting of step (4) is carried out, it can first pass through often
Drying is advised, the product of roasting intensity so obtained is more preferable.
In above-mentioned technical proposal, organic amine selects aniline, and carries out step (1) (2) (3) (4) in order, can prepare catalysis
Agent A, namely the above-mentioned molybdenum carbide in XRD powder diagrams with feature (a).
In above-mentioned technical proposal, organic amine selects 1,6- hexamethylene diamines, before the roasting for carrying out step (4), will obtain material
III dissipated again with moisture of 10~30 times equivalent to its dry weight, and adds ammonium persulfate (APS), and dosage can be material
0.1~1.5 times of III dry weights, regulation pH value of solution is to 2~3.5, then carries out step (4), can prepare catalyst B, Ye Jishang
State has the molybdenum carbide of feature (b) in XRD powder diagrams.
In above-mentioned technical proposal, organic amine selects TEPA, and carries out step (1) (2) (3) (4) in order, can make
Standby catalyst C, namely the above-mentioned molybdenum carbide in XRD powder diagrams with feature (c).
In above-mentioned technical proposal, organic amine selects aniline, and the molybdenum source aqueous solution in step (1) also contains cetyl
Trimethylammonium bromide (CTAB), in mol CTAB:Mo atoms are 0.01~10 times, and continue to carry out step (2) (3) in order
(4) catalyst D, namely the above-mentioned molybdenum carbide in XRD powder diagrams with feature (d) can, be prepared.
In above-mentioned technical proposal, described molybdenum source is preferably the water soluble salt of the oxyacid of molybdenum.
In above-mentioned technical proposal, described water soluble salt preferably is selected from ammonium salt, alkali metal salt, calcium salt, magnesium salts, thallium salt and zinc salt
At least one of.
In above-mentioned technical proposal, the oxyacid of described molybdenum preferably is selected from positive molybdic acid, metamolybdic acid, para-molybdic acid, two molybdic acids and four
At least one of molybdic acid.
As non-restrictive：
In above-mentioned technical proposal, step (1) is not particularly limited for adjusting pH acid, but economically sees that inorganic acid is excellent
In organic acid, conventional inorganic acid can be hydrochloric acid, sulfuric acid, nitric acid etc.；The concentration of inorganic acid is preferably 0.1~5.0mol/L.
It is used in step (4) that molybdenum carbide is not particularly limited in chemically inert atmosphere in above-mentioned technical proposal, as
Non-restrictive, the atmosphere inert to molybdenum carbide can be inert gas (the such as, but not limited to helium in the periodic table of elements
Gas, argon gas), nitrogen, at least one of carbon monoxide and methane or their mixture.
In above-mentioned technical proposal, sintering temperature is preferably 650~750 DEG C in step (4), and roasting time is 2~8 hours；
Further preferred sintering temperature is 650~750 DEG C, roasting time 6~16 hours.
In order that catalyst pattern is more perfect, the preroast stage comprised the following steps is preferably undergone before firing：From
Room temperature starts to be warming up to 250~350 DEG C with 4~10 DEG C/min speed, is then warming up to 1~3 DEG C/min speed above-mentioned
Sintering temperature.
Because molybdenum carbide activity is stronger, it is easy to air contact and vigorous oxidation reaction occurs, big calorimetric is released after spontaneous combustion, so
Need to be passivated processing before XRD and SEM is characterized, passivating conditions are：In by volume oxygenous 0.5~5% oxygen-nitrogen
In mixed atmosphere, temperature is 0~50 DEG C, is handled 2~24 hours.
But the catalyst sample for hydrogenation reaction can be directly used in hydrogenation reaction without Passivation Treatment, in order to store
Transportation safety is it is also contemplated that passivation, but because the catalyst activity after passivation is relatively low, the catalyst that Passivation Treatment is crossed can be
Contain methane-hydrogen mixed gas activation process for being used again before hydrogenation reaction, such as the condition of activation process is：First by volume
The content of methane is 10~30% in alkane-hydrogen mixed gas, 550~650 DEG C for the treatment of temperature, and processing time is 2~6 hours.
Catalyst in the specific embodiment of the invention for hydrogenation reaction is not pass through Passivation Treatment.
The key problem in technology of the present invention is the selection of catalyst, and those skilled in the art can be according to the note of description of the invention
Carry the process conditions for rationally determining reaction.As non-restrictive：
Catalyst amount can be but be not limited to the 1~50% of citral weight.
Hydrogenation reaction solvent can be 3~8 times of citral weight.
Hydrogenation reaction solvent can be toluene, tetrahydrofuran, ethanol, isopropanol, petroleum ether or its mixture.
Hydrogenation reaction temperature can be 90~130 DEG C.
Reaction pressure can be 1~5MPa.
Reaction time can be 5~10 hours.
To solve the three of above-mentioned technical problem, technical scheme is as follows：Technical side described in one of technical problem
Molybdenum carbide catalyst any one of case the answering as catalyst in citral Hydrogenation nerol and geraniol reaction
With.
The present inventor has surprisingly found that, molybdenum carbide of the XRD powder diagrams with feature listed by above-mentioned (b) with
To the finer selection of nerol and geraniol (in terms of nerol and geraniol overall selectivity)；XRD powder diagrams have upper
The molybdenum carbide of feature listed by (c) is stated with the higher receipts to nerol and geraniol (in terms of nerol and geraniol total recovery)
Rate.
Baking oven or the temperature of oil bath be concretely in above-mentioned steps (4)：40,45,50,55,60,65 or 70 DEG C；During reaction
Between concretely：4,6,8,10,12,14,16,18,20,22 or 24 hours；
Sintering temperature is specifically as follows in above-mentioned steps (4)：650,675,690,700,715,725,735 or 750 DEG C；It is permanent
Warm roasting time is specifically as follows 2,4,6 or 8 hours.
On the basis of such scheme, molybdate is ammonium molybdate, potassium molybdate, sodium molybdate or zinc molybdate in step (1).
Relatively existing catalyst, the present invention have the advantage that：
(1) noble metal component is free of in catalyst, cost is low, economy is high, stock number is wide.
(2) application of transition metal carbide catalyst, the reaction of alternative precious metal catalyst are effectively extended.
(3) preparation condition is simple and easy to control, and technique simplifies, and cost is relatively low, and product quality is higher, and stability is good, and atom utilizes
Rate is high, environment-friendly.
(4) hydrogenation conditions are gentle, require relatively low to facility environment and operation.
Brief description of the drawings
Fig. 1 is catalyst A used herein XRD powder diagrams；
Fig. 2 is catalyst B used herein XRD powder diagrams；
Fig. 3 is catalyst C used herein XRD powder diagrams；
Fig. 4 is catalyst D used herein XRD powder diagrams.
Embodiment
【Embodiment 1】
1st, catalyst preparation
Take (the NH that 0.07mol/L is calculated as with molybdenum atom concentration4)6Mo7O24·4H2O aqueous solution 0.15L, are added into solution
0.18mol aniline, the lower HCl solution for instilling 2mol/L of stirring to pH=2.0 obtain material I；
In 60 DEG C of stewing process material II is obtained for 12 hours to material I, filters, filter cake is washed with water and uses water every time three times
200mL, then washing filter cake with absolute ethyl alcohol and use ethanol 100mL every time three times, last filter cake is dried in vacuo 12 hours at 60 DEG C,
Obtain material III.
Material III preroast and roastings in a nitrogen atmosphere：With 5 DEG C/min heating rate 300 DEG C are risen to by 20 DEG C, then
700 DEG C are risen to by 300 DEG C with 1 DEG C/min heating rate, is kept for 2 hours at a temperature of 700 DEG C.Room temperature is down to afterwards, in nitrogen
Cooled down 48 hours under gas shielded, obtain required molybdenum carbide catalyst A.
XRD powder diagrams are shown in Fig. 1, and its diffraction maximum position having and strength characteristic are as follows：
Peak position：θ=37.2 ° of 1a peaks 2, θ=42.2 ° of 2a peaks 2, θ=61.8 ° of 3a peaks 2, θ=74.3 ° of 4a peaks 2；
Peak intensity ratio：1a:2a=1.75:1,1a:3a=2.1:1,1a:4a=2.1:1.
2nd, hydrogenation reaction
Citral catalysis selective hydrogenation reaction is carried out in the 100mL batch autoclaves with stirring.Added into kettle
6g toluene (AR, traditional Chinese medicines chemical reagent) is used as reaction dissolvent, adds catalyst A 0.5g under nitrogen protection rapidly.Again into kettle
Addition reaction raw materials citral 1.5g (97%, cis+trans, Aladdin), it is eventually adding isopropanol 6g (AR, traditional Chinese medicines chemistry examination
Agent), stirring is sufficiently mixed it.With the air in hydrogen replacement reaction kettle three times.It is 3.0MPa to adjust hydrogen pressure in kettle, heating temperature
Spend for 100 DEG C, stir speed (S.S.) 300rpm, 5 hours reaction time.Reaction is cooled to room temperature after terminating, it is anhydrous to add internal standard compound
Ethanol 1.5g (AR, traditional Chinese medicines chemical reagent), it is well mixed extract reaction solution centrifugation after take supernatant liquor, with gas-chromatography to form into
Row analysis.
Chromatographic condition is as follows：
Chromatogram model：Agilent 6890N type gas-chromatographies, HP-5 capillary columns (30m × 0.32mm × 0.25 μm), match somebody with somebody
Put flame ionization ditector (FID), combustion gas H2, flow 40mL/min, air is combustion-supporting gas, flow 400mL/
Min, protection gas are helium, flow 1.5mL/min.230 DEG C of injector temperature, pressure 30psi.
The reaction result of molybdenum carbide catalyst A Selective hydrogenation of citral nerol and geraniol is as follows：React 5 hours
Conversion ratio is 89%, and selectivity (in terms of nerol and geraniol total amount) is 37%, yield 32.93%.
【Embodiment 2】
1st, catalyst preparation
Take (the NH that 0.07mol/L is calculated as with molybdenum atom concentration4)6Mo7O24·4H2O aqueous solution 0.15L, are added into solution
0.18mol 1,6- hexamethylene diamine, the lower HCl solution for instilling 2mol/L of stirring to pH=2.0 obtain material I；
In 60 DEG C of stewing process material II is obtained for 12 hours to material I, filters, filter cake is washed with water and uses water every time three times
200mL, then washing filter cake with absolute ethyl alcohol and use ethanol 100mL every time three times, last filter cake is dried in vacuo 12 hours at 60 DEG C,
Obtain material III.
Take 3.39g materials III to be suspended in 100mL water, add 1.45g APS, stir the lower HCl solution for instilling 2mol/L
To pH=2.5, filtering, filter cake is washed with water and uses water 200mL every time three times, last filter cake is dried in vacuo 12 hours at 60 DEG C, obtained
Material IIIB
Material IIIB preroast and roastings in a nitrogen atmosphere：300 DEG C are risen to by 20 DEG C with 5 DEG C/min heating rate,
700 DEG C are risen to by 300 DEG C with 1 DEG C/min heating rate again, is kept for 2 hours at a temperature of 700 DEG C.Room temperature is down to afterwards,
The lower cooling of nitrogen protection 48 hours, obtain required molybdenum carbide catalyst B.
XRD powder diagrams are shown in Fig. 2, and its diffraction maximum position having and strength characteristic are as follows：
Peak position：θ=34.3 ° of 1b peaks 2, θ=37.9 ° of 2b peaks 2, θ=39.3 ° of 3b peaks 2, θ=52.1 ° of 4b peaks 2, the θ of 5b peaks 2
=61.5 °, θ=69.5 ° of 6b peaks 2, θ=72.4 ° of 7b peaks 2, θ=74.6 ° of 8b peaks 2, θ=75.6 ° of 9b peaks 2；
Peak intensity ratio：1b:2b=1.2:1,1b:3b=0.3:1,1b:4b=2.3:1,1b:5b=1.4:1,1b:6b=
2.3:1,1b:7b=4.5:1,1b:8b=1.6:1,1b:9b=1.9:1.
2nd, hydrogenation reaction
Citral catalysis selective hydrogenation reaction is carried out in the 100mL batch autoclaves with stirring.Added into kettle
6g toluene (AR, traditional Chinese medicines chemical reagent) is used as reaction dissolvent, adds catalyst B 0.5g under nitrogen protection rapidly, prevents from exposing
Air time is longer to cause catalyst oxidative deactivation.Added again into kettle reaction raw materials citral 1.5g (97%, cis+trans,
Aladdin), isopropanol 6g (AR, traditional Chinese medicines chemical reagent) is eventually adding, stirring is sufficiently mixed it.The charge and discharge repeatedly into reactor
Hydrogen enters line replacement three times, to oxygen therein.Hydrogen pressure is 3.0MPa in regulation kettle, and heating-up temperature is 100 DEG C, and stir speed (S.S.) is
300rpm, 5 hours reaction time.Reaction is cooled to room temperature after terminating, add internal standard compound absolute ethyl alcohol 1.5g (AR, traditional Chinese medicines chemistry
Reagent), it is well mixed after extracting reaction solution centrifugation and takes supernatant liquor, composition is analyzed with gas-chromatography, chromatographiccondition
With embodiment 1.
The reaction result of molybdenum carbide catalyst B Selective hydrogenation of citral nerol and geraniol is as follows：React 5 hours
Conversion ratio is 45%, and selectivity (in terms of nerol and geraniol total amount) is 77%, yield 34.65%.
【Embodiment 3】
1st, catalyst preparation
Take (the NH that 0.07mol/L is calculated as with molybdenum atom concentration4)6Mo7O24·4H2O aqueous solution 0.15L, are added into solution
0.18mol TEPAs, the lower HCl solution for instilling 2mol/L of stirring to pH=2.0 obtain material I.
In 60 DEG C of stewing process material II is obtained for 12 hours to material I, filters, filter cake is washed with water and uses water every time three times
200mL, then washing filter cake with absolute ethyl alcohol and use ethanol 100mL every time three times, last filter cake is dried in vacuo 12 hours at 60 DEG C,
Obtain material III.
Material III preroast and roastings in a nitrogen atmosphere：With 5 DEG C/min heating rate 300 DEG C are risen to by 20 DEG C, then
700 DEG C are risen to by 300 DEG C with 1 DEG C/min heating rate, is kept for 2 hours at a temperature of 700 DEG C.Room temperature is down to afterwards, in nitrogen
Cooled down 48 hours under gas shielded, obtain required molybdenum carbide catalyst C.
XRD powder diagrams are shown in Fig. 3, and its diffraction maximum position having and strength characteristic are as follows：
Peak position：θ=37.3 ° of 1c peaks 2, θ=43.2 ° of 2c peaks 2, θ=63.1 ° of 3c peaks 2, θ=75.7 ° of 4c peaks 2；
Peak intensity ratio：1c:2c=2.1:1,1c:3c=2.9:1,1c:4c=3.5:1.
2nd, hydrogenation reaction
Citral catalysis selective hydrogenation reaction is carried out in the 100mL batch autoclaves with stirring.Added into kettle
6g toluene (AR, traditional Chinese medicines chemical reagent) is used as reaction dissolvent, adds catalyst C 0.5g under nitrogen protection rapidly, prevents from exposing
Air time is longer to cause catalyst oxidative deactivation.Added again into kettle reaction raw materials citral 1.5g (97%, cis+trans,
Aladdin), isopropanol 6g (AR, traditional Chinese medicines chemical reagent) is eventually adding, stirring is sufficiently mixed it.The charge and discharge repeatedly into reactor
Hydrogen enters line replacement three times, to oxygen therein.Hydrogen pressure is 3.0MPa in regulation kettle, and heating-up temperature is 100 DEG C, and stir speed (S.S.) is
300rpm, 5 hours reaction time.Reaction is cooled to room temperature after terminating, add internal standard compound absolute ethyl alcohol 1.5g (AR, traditional Chinese medicines chemistry
Reagent), it is well mixed after extracting reaction solution centrifugation and takes supernatant liquor, composition is analyzed with gas-chromatography, chromatographiccondition
With embodiment 1.
The reaction result of molybdenum carbide catalyst C Selective hydrogenation of citral nerol and geraniol is as follows：React 5 hours
Conversion ratio is 86%, and selectivity (in terms of nerol and geraniol total amount) is 58%, yield 49.88%.
【Embodiment 4】
1st, catalyst preparation
Take (the NH that 0.07mol/L is calculated as with molybdenum atom concentration4)6Mo7O24·4H2O aqueous solution 0.15L, the molybdenum source aqueous solution is also
Containing the cetyl trimethylammonium bromide (CTAB) that molar concentration is 0.07mol/L, 0.18mol aniline is added into solution,
The lower HCl solution for instilling 2mol/L of stirring obtains material I to pH=2.0；
In 60 DEG C of stewing process material II is obtained for 12 hours to material I, filters, filter cake is washed with water and uses water every time three times
200mL, then washing filter cake with absolute ethyl alcohol and use ethanol 100mL every time three times, last filter cake is dried in vacuo 12 hours at 60 DEG C,
Obtain material III.
Material III preroast and roastings in a nitrogen atmosphere：With 5 DEG C/min heating rate 300 DEG C are risen to by 20 DEG C, then
700 DEG C are risen to by 300 DEG C with 1 DEG C/min heating rate, is kept for 2 hours at a temperature of 700 DEG C.Room temperature is down to afterwards, in nitrogen
Cooled down 48 hours under gas shielded, obtain required molybdenum carbide catalyst D.
XRD powder diagrams are shown in Fig. 4, and its diffraction maximum position having and strength characteristic are as follows：
Peak position：θ=26.0 ° of 1d peaks 2, θ=34.4 ° of 2d peaks 2, θ=36.9 ° of 3d peaks 2, θ=37.9 ° of 4d peaks 2, the θ of 5d peaks 2
=39.4 °, θ=52.1 ° of 6d peaks 2, θ=53.6 ° of 7d peaks 2, θ=61.6 ° of 8d peaks 2, θ=69.5 ° of 9d peaks 2, the θ of 10d peaks 2=
72.6 °, θ=74.6 ° of 11d peaks 2, θ=75.5 ° of 12d peaks 2；
Peak intensity ratio：1d:2d=0.5:1,1d:3d=0.75:1,1d:4d=0.6:1,1d:5d=0.18:1,1d:6d
=1:1,1d:7d=1.6:1,1d:8d=0.6:1,1d:9d=1.1:1,1d:10d=2:1,1d:11d=1.4:1,1d:12d
=1:1.
2nd, hydrogenation reaction
Citral catalysis selective hydrogenation reaction is carried out in the 100mL batch autoclaves with stirring.Added into kettle
6g toluene (AR, traditional Chinese medicines chemical reagent) is used as reaction dissolvent, adds catalyst D 0.5g under nitrogen protection rapidly, prevents from exposing
Air time is longer to cause catalyst oxidative deactivation.Added again into kettle reaction raw materials citral 1.5g (97%, cis+trans,
Aladdin), isopropanol 6g (AR, traditional Chinese medicines chemical reagent) is eventually adding, stirring is sufficiently mixed it.The charge and discharge repeatedly into reactor
Hydrogen enters line replacement three times, to oxygen therein.Hydrogen pressure is 3.0MPa in regulation kettle, and heating-up temperature is 100 DEG C, and stir speed (S.S.) is
300rpm, 5 hours reaction time.Reaction is cooled to room temperature after terminating, add internal standard compound absolute ethyl alcohol 1.5g (AR, traditional Chinese medicines chemistry
Reagent), it is well mixed after extracting reaction solution centrifugation and takes supernatant liquor, composition is analyzed with gas-chromatography, chromatographiccondition
With embodiment 1.
The reaction result of molybdenum carbide catalyst D Selective hydrogenation of citral nerol and geraniol is as follows：React 5 hours
Conversion ratio is 58%, and selectivity (in terms of nerol and geraniol total amount) is 64%, yield 37.12%.
Claims (9)
1. for citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol：The XRD diffraction of the molybdenum carbide catalyst
Spectrogram has one kind in following four kinds of features：
(a) peak position：θ=36~38 ° of 1a peaks 2, θ=41~43 ° of 2a peaks 2, θ=61~63 ° of 3a peaks 2, θ=73 of 4a peaks 2~
75°；
Peak intensity ratio：1a:2a=1~2:1,1a:3a=1.5~3:1,1a:4a=1.5~3:1；
(b) peak position：θ=34~35 ° of 1b peaks 2, θ=37~38 ° of 2b peaks 2, θ=39~40 ° of 3b peaks 2, θ=51 of 4b peaks 2~
53 °, θ=61~63 ° of 5b peaks 2, θ=69~71 ° of 6b peaks 2, θ=72~73 ° of 7b peaks 2, θ=74~75 ° of 8b peaks 2, the θ of 9b peaks 2=
75~76 °；
Peak intensity ratio：1b:2b=1~2:1,1b:3b=0.2~0.6:1,1b:4b=1.5~3:1,1b:5b=0.8~1.5:
1,1b:6b=1.5~3:1,1b:7b=3~7:1,1b:8b=1~3:1,1b:9b=1.5~3:1；
(c) peak position：θ=36~39 ° of 1c peaks 2, θ=42~44 ° of 2c peaks 2, θ=62~65 ° of 3c peaks 2, θ=74 of 4c peaks 2~
77°；
Peak intensity ratio：1c:2c=1.5~2.5:1,1c:3c=2.5~3.5:1,1c:4c=3~4:1；
(d) peak position：θ=25~27 ° of 1d peaks 2, θ=34~35 ° of 2d peaks 2, θ=36~37 ° of 3d peaks 2, θ=37 of 4d peaks 2~
39 °, θ=39~41 ° of 5d peaks 2, θ=51~53 ° of 6d peaks 2, θ=53~54 ° of 7d peaks 2, θ=61~63 ° of 8d peaks 2, the θ of 9d peaks 2=
68~70 °, θ=71~73 ° of 10d peaks 2, θ=73.5~75 ° of 11d peaks 2, θ=75~77 ° of 12d peaks 2；
Peak intensity ratio：1d:2d=0.1~2:1,1d:3d=0.2~2:1,1d:4d=0.2~2.5:1,1d:5d=0.1~
1.5:1,1d:6d=0.5~2:1,1d:7d=0.5~2:1,1d:8d=0.1~2:1,1d:9d=0.5~2:1,1d:10d
=0.5~3:1,1d:11d=0.2~2:1,1d:12d=0.5~2:1.
2. the preparation method of catalyst according to claim 1, comprises the following steps：
(1) organic amine is added in the aqueous solution of molybdenum source and be well mixed, be 0.5~6.5 with acid for adjusting pH, obtain containing flocculent deposit
The material I of thing；
(2) the material I is carried out being thermally treated resulting in material II；
(3) material II progress separation of solid and liquid is obtained into solid material III；
(4) it is being in be calcined to obtain the catalyst in chemically inert atmosphere to molybdenum carbide.
3. preparation method according to claim 2, it is characterised in that described molybdenum source is the water soluble salt of the oxyacid of molybdenum.
4. preparation method according to claim 3, it is characterised in that described water soluble salt be selected from ammonium salt, alkali metal salt,
At least one of calcium salt, magnesium salts, thallium salt and zinc salt.
5. preparation method according to claim 3, it is characterised in that the oxyacid of described molybdenum is selected from positive molybdic acid, inclined molybdenum
At least one of acid, para-molybdic acid, two molybdic acids and four molybdic acids.
6. preparation method according to claim 2, it is characterised in that：In step (1) be used for adjust pH acid be selected from hydrochloric acid,
Nitric acid or sulfuric acid.
7. preparation method according to claim 2, it is characterised in that：The gas inert to molybdenum carbide used in step (4)
Atmosphere is selected from least one of inert gas, nitrogen, carbon monoxide and methane or their mixture.
8. preparation method according to claim 2, it is characterised in that：Sintering temperature is 650~750 DEG C in step (4), roasting
It is 2~8 hours to burn the time.
9. the molybdenum carbide catalyst described in claim 1 is used as catalyst in citral Hydrogenation nerol and geraniol reaction
Application.
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