CN106311238A - Preparation method and use of liquid phase aldehyde hydrogenation catalyst - Google Patents
Preparation method and use of liquid phase aldehyde hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a high-efficiency liquid phase aldehyde hydrogenation cobalt metal catalyst and a preparation method thereof. The method is suitable for preparing a cobalt system liquid phase hydrogenation catalyst through an impregnation technology. The method comprises the following steps: adding an active carbon carrier to an aqueous cobalt salt solution A, stirring the carrier and the solution, carrying out water bath treatment, drying the treated mixture to obtain an unformed catalyst, uniformly dropwise adding a potassium borohydride solution to the unformed catalyst, washing the obtained material, drying the washed material to obtain a catalyst precursor, introducing nitrogen and hydrogen to the catalyst precursor, and carrying out roasting activation to obtain the catalyst. The catalyst obtained in the invention has the advantages of very high activity, very high specific surface area, realization of high-efficiency catalysis of liquid phase aldehyde (propionaldehyde, butyraldehyde, isobutyraldehyde and octenal) hydrogenation, and good industrial application prospect.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to the preparation method of efficient liquid phase aldehyde hydrogenating catalyst.
Background technology
The features such as the aldehyde field of hydrogenation at current chemical industry is widely used with nickel for main active i.e. nickel catalyst, and it is low that this catalyst has hydrogenation activity temperature, and operation energy consumption is few.The octenal liquid phase hydrogenating catalyst that Jilin Chemical company academy develops at home is applied on chemical fertilizer factory of Jilin Chemical Industrial Co. Ltd. butyl octanol unit.Developing nickel system aldehyde hydrogenation company abroad and have German BASF, its catalyst is with nickel as main active, and to add alkaline-earth metal magnesium be auxiliary agent aldehyde hydrogenating catalyst.The Ni system Ni-ZrO/SiO that Hoechst company of Germany develops2Aldehyde hydrogenating catalyst.Japan three insults in the senior aldehyde hydrogenating catalyst of Ni system that chemical company develops and with the addition of Cr as auxiliary agent.Russia's Grevich Gs patent EP, 3667 describe two-step method produces octyl alconyl technique and catalyst thereof, adds Cr as auxiliary agent in its Ni system liquid-phase hydrogenatin catalyst for refining.But above-mentioned catalyst there will be the problems such as more by-product in process of production.
Also occur in that employing chemical reduction method prepares ultrafine particle amorphous alloy catalyst in some patents at present, it is many that this type catalyst has surface activity atom, surface area is big, the feature high with surface energy, add the shortrange order of amorphous alloy, the construction features of longrange disorder, makes it have very high catalytic activity and selectivity.Use amorphous alloy can be effectively improved catalysis activity and selectivity, but superfine catalyst separates difficulty with product, and reactor plugs may be caused.
Summary of the invention
The present invention seeks to: preparation method and the purposes of a kind of preparing alcohol catalyst through adding hydrogen to aldehyde with activated carbon as carrier and metal cobalt loaded are provided.
The present invention is mainly characterized by: uses infusion process to make cobalt be highly dispersed in activated carbon surface, then passes through KBH4Make Co2+Ion reduction becomes Co0, and form fresh load type Co-B amorphous alloy catalyst.Catalyst prepared by such method can be effectively improved catalyst activity and selectivity during aldehyde hydrogenation reaction.The simple row of this preparation method, it is easy to industry is amplified, it is adaptable to the hydrogenation of propionic aldehyde, butyraldehyde, isobutylaldehyde, octenal under lower pressure.
The present invention provides cobalt metallic catalyst preparation method, comprises the steps,
(1) absorbent charcoal carrier AC is joined in cobalt saline solution A, stir under water bath condition, then dry the non-adult B obtaining catalyst；
(2) at room temperature 30 minutes introversion non-adult B drip solution of potassium borohydride, control the addition of solution of potassium borohydride, make KBH4Being 41 with the amount ratio of the material of Co, water washing, drying obtain catalyst precarsor C；
(3) catalyst precarsor C is led to after nitrogen hydrogen firing 13 hours activation catalyst adult Co-B AC.
The present invention is to join in solution A by absorbent charcoal carrier, water-bath, stir, dry the non-adult B obtaining catalyst.Under room temperature condition, slowly by 160ml in 30 minutes
2mol/L KBH4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B, wherein KBH of catalyst4It is 41 with the amount ratio of the material of Co, can ensure that all of Co is all completely reduced in course of reaction and has substantial amounts of gas release and produce black solid, after question response terminates, the precursor C of catalyst is obtained with water cyclic washing, drying, then catalyst precarsor C is led to nitrogen hydrogen, and obtain after roasting activation in 13 hours the most at different temperatures Co-B that relevant temperature processes AC catalyst adult.
Described cobalt salt concretely Co (NO3)2、CoSO4、CoCl2、Co(CH3COO)2In at least one, preferably Co (NO3)2. 。In described solution A, the concentration of cobalt ion concretely 10 80mmol/L.
The temperature of described water-bath can be 60 DEG C 95 DEG C, concretely 90 DEG C 95 DEG C.
The temperature of described drying is 80 DEG C 120 DEG C, concretely 100 DEG C 120 DEG C.
After described method also including absorbent charcoal carrier is added solution A, the step being stirred.
The time stirred can be less than 1-12 hour, concretely 12 hours.
Described method also includes the step that catalyst is carried out activate.Described activation can be by catalyst precarsor in hydrogen and nitrogen, and 200 DEG C-700 DEG C process 0.5 12 hours, by specifically coming at a temperature of place ought to be 350 DEG C-450 DEG C 13 hours
Gas flow 30 100ml/min, concretely 40 50ml/min being passed through in described activation.
The cobalt supported active Pd/carbon catalyst that the present invention provides, the weight/mass percentage composition 15 50 of metal.
The cobalt metallic catalyst of present invention highly disperse active charcoal loads, and high degree of dispersion i.e. has more than 150m2/ g, even 260m2/ g cobalt surface area.
The present invention uses the carried non-crystal alloy catalyst of activated carbon supported metal cobalt, can reduce side reaction product and produce, and is catalyzed activity and selectivity during being effectively improved aldehyde hydrogenation reaction.There is good industrial applications prospect.
Detailed description of the invention
Specific examples below is easy to be best understood from the present invention, but does not limit the present invention, and the test method in enforcement, without specified otherwise, is conventional method, test material used in this enforcement, if no special instructions, is and is commercially available from routine biochemistry reagent shop.Tests below is all provided with three times and repeats, and result takes average.
One. absorbent charcoal carrier selects and preparation
Original coconut husk charcoal and almond charcoal (activated carbon limit company of Beijing brilliance crystalline substance section) are broken into the powder of 20～40 mesh, and in 100 DEG C of drying after washing, the sample of gained is designated as AC respectively1And AC2. all catalyst are all prepared with vacuum impregnation technology.
Two. the preparation of catalyst and activity rating thereof
Embodiment 1
1. the preparation of catalyst precarsor
By 1.5gCo (NO3)2·6H2O is dissolved in during 100ml anhydrates, and adds 2.9g absorbent charcoal carrier AC1, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 350 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 2
1. the preparation of catalyst precarsor
By 1.5g Co (NO3)2·6H2O is dissolved in 100ml water, adds 2.9g absorbent charcoal carrier AC2, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 350 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 3
1. the preparation of catalyst precarsor
By 1.5g Co (NO3)2·6H2O is dissolved in 100ml water, adds 2.9g absorbent charcoal carrier AC1, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.After being cooled to room temperature and at ambient temperature, slowly by 160ml 2mol/L KBH in 30 minutes4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B of catalyst, after question response terminates, with water cyclic washing repeatedly, is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 350 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 4
1. the preparation of catalyst precarsor
By 1.5gCo (NO3)2·6H2O is dissolved in 100ml water, adds 2.9g absorbent charcoal carrier AC2, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.After being cooled to room temperature and at ambient temperature, slowly by 160ml 2mol/L KBH in 30 minutes4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B of catalyst, after question response terminates, with water cyclic washing repeatedly, is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 350 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 5
1. the preparation of catalyst precarsor
By 1.5gCo (NO3)2·6H2O is dissolved in during 100ml anhydrates, and adds 2.9g absorbent charcoal carrier AC1, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.After being cooled to room temperature and at ambient temperature, slowly by 160ml, 2mol/L KBH in 30 minutes4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B of catalyst, after question response terminates, with water cyclic washing repeatedly, is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 450 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 6
1. the preparation of catalyst precarsor
By 1.5gCo (NO3)2·6H2O is dissolved in during 100ml anhydrates, and adds 2.9g absorbent charcoal carrier AC1, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.After being cooled to room temperature and at ambient temperature, slowly by 160ml, 2mol/L KBH in 30 minutes4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B of catalyst, after question response terminates, with water cyclic washing repeatedly, is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 450 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 7
1. the preparation of catalyst precarsor
By 1.5gCo (NO3)2·6H2O is dissolved in during 100ml anhydrates, and adds 2.9g absorbent charcoal carrier AC2, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.After being cooled to room temperature and at ambient temperature, slowly by 160ml, 2mol/L KBH in 30 minutes4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B of catalyst, after question response terminates, with water cyclic washing repeatedly, is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 600 DEG C of activation 2h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Embodiment 8
1. the preparation of catalyst precarsor
By 1.5gCo (NO3)2·6H2O is dissolved in during 100ml anhydrates, and adds 2.9g absorbent charcoal carrier AC1, magnetic stirring 2h in 95 DEG C of water-baths, it is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.After being cooled to room temperature and at ambient temperature, slowly by 160ml, 2mol/L KBH in 30 minutes4, solution (including 0.2mol/L NaOH) is added drop-wise to the non-adult B of catalyst, after question response terminates, with water cyclic washing repeatedly, is subsequently placed in 110 DEG C of baking ovens (being full of nitrogen) and dries 12h.
2. the preparation of catalyst
Catalyst precarsor 120mg step 1 obtained loads in ∪ type quartz ampoule, and in hydrogen nitrogen mixed gas, 600 DEG C of activation 3h, the flow of hydrogen and nitrogen is 20ml/min.Activation rear catalyst evaluation result is shown in Table 1.
Three. catalyst activity evaluation and the evaluation of catalyst performance
1. the mensuration of the metal specific surface area of catalyst, the results are shown in Table 1.
Owing in catalyst, metal is cobalt.According to the size of metal surface area in cobalt tenor estimation metallic catalyst, the computational methods of metal surface area are as follows:
Cobalt metal surface area=(6.023 × 1023× V × SF × A)/22414:
Wherein V is CO chemisorbed amount, and SF is stoichiometric factor, it is assumed that SF=1, and i.e. one the corresponding movable metallic site of CO molecule, A is cobalt atom footprint area, takes 0.062nm2。
The method of this calculating metal surface area sees Micromeretics
ASAP2010 Chemisystemv.3 workbook (part number；(201-42808-01, March calendar year 2001), appendix C.
CO chemisorbed quantity measuring method is as follows: about 0.1 gram of catalyst, logical H2At 350 DEG C of reduction 1h, then at 350 DEG C of evacuation 3h, 350 DEG C of evacuation 1h, CO are chemisorbed on 35 DEG C to be carried out, and surveys adsorption curve in 50-500Toor pressure limit, is extended to obtain chemisorbed value when pressure is 0 by twice absorption difference curve of test.
2. specific surface area active measures, and the results are shown in Table 1.
Specific surface area active (Sact) measured by hydrogen adsorption instrument (CHEMBET-3000, Quantachrome), sample is in high-purity N2: air-flow purges 2h at 473 K, the most at room temperature makes H2Pulsed Sampling, until catalyst no longer adsorbs hydrogen and reaches adsorption equilibrium.Use similar analysis, see Journal of Molecular Catalysis volume 21 the 1st phase 43-47 page.
3. catalyst performance evaluation
In 200ml reactor, add above-mentioned steps gained catalyst 0.6g, 40ml spirit solvent, 4ml hutanal, be passed through hydrogen 4-5 time to replace gas reactor, be finally passed through hydrogen and reach 1MP to pressure in stilla, temperature of reaction kettle is slowly increased to 100 DEG C, in heating process, in reactor, pressure also gradually rises up to 1MPaRear turn on agitator, now hydrogenation reaction starts, and for eliminating the spreading effect impact on kinetics, control mixing speed is more than 800rpm, and during observing response, the change of Hydrogen Vapor Pressure is to calculate hydrogen-absorption speed.Record front 30
In min, hydrogen pressure fall, records specific surface area active according to hydrogen adsorption.Every 30 min samplings in course of reaction, after reaction 4h, gained product is by gas chromatogram (9890, FID) product analysis is carried out to determine conversion ratio and selectivity, using Agilent company 4890 type chromatographic product composition, the senior capillary column of QC3/AC20-10 type (SGE company) FID detects.It is shown in Table 1 by above-mentioned condition activation rear catalyst evaluation result.
。
Claims (9)
1. the preparation method of a liquid phase aldehyde hydrogenating catalyst, it is characterised in that specifically include step:
(1) absorbent charcoal carrier AC is joined in cobalt saline solution A, stir under water bath condition, then dry the non-adult B obtaining catalyst；
(2) at room temperature 30 minutes introversion non-adult B drip solution of potassium borohydride (including 0.2mol/L NaOH), control the addition of solution of potassium borohydride, make KBH4Being 41 with the amount ratio of the material of Co, water washing, drying obtain catalyst precarsor C；
(3) catalyst precarsor C is led to after nitrogen hydrogen firing 13 hours activation catalyst adult Co-B AC.
2. the method for claim 1, it is characterised in that described cobalt salt is Co (NO3)2、CoSO4、CoCl2、Co (CH3COO)2In at least one, in described solution A, the concentration of cobalt ion is 10 80mmol/L.
3. the method for claim 1, it is characterised in that described mixing time is 1 12 hours, described bath temperature is 60 DEG C 95 DEG C.
4. the method for claim 1, it is characterised in that described drying temperature is 80 DEG C 120 DEG C.
5. the method for claim 1, it is characterised in that described sintering temperature is 200 DEG C 700 DEG C.
6. the method for claim 1, it is characterised in that the logical nitrogen hydrogen flowing quantity of described activation is 10 100ml/min.
7. the method for claim 1, it is characterised in that the cobalt supported active Pd/carbon catalyst of preparation, the weight/mass percentage composition 15 50 of metal.
8. the method for claim 1, it is characterised in that described activated carbon is coconut husk charcoal and almond charcoal.
9. the method for claim 1, it is characterised in that the Co-B of preparation AC liquid phase aldehyde hydrogenating catalyst, it is adaptable to propionic aldehyde, butyraldehyde, isobutylaldehyde, the hydrogenation reaction of octenal.
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Cited By (1)
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| CN110433807A (en) * | 2019-07-23 | 2019-11-12 | 山西新华化工有限责任公司 | It is a kind of to carry Co catalysts material and preparation without ammono-system for protect cyanogen chloride |
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| CN110433807A (en) * | 2019-07-23 | 2019-11-12 | 山西新华化工有限责任公司 | It is a kind of to carry Co catalysts material and preparation without ammono-system for protect cyanogen chloride |
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