CN1541763A - Amorphous catalyst with cobalt and boron for crotonaldehyde hydrogenation and its preparation - Google Patents

Amorphous catalyst with cobalt and boron for crotonaldehyde hydrogenation and its preparation Download PDF

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CN1541763A
CN1541763A CNA2003101084379A CN200310108437A CN1541763A CN 1541763 A CN1541763 A CN 1541763A CN A2003101084379 A CNA2003101084379 A CN A2003101084379A CN 200310108437 A CN200310108437 A CN 200310108437A CN 1541763 A CN1541763 A CN 1541763A
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catalyst
cobalt
preparation
catalyzer
boron
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CN100475334C (en
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乔明华
裴燕
胡华荣
范康年
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Fudan University
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Abstract

The present invention relates to chemical technology, and is especially novel non-crystal catalyst for hydrogenating crotonaldehyde into crotyl alcohol and its preparation. The catalyst consists of Co, B and modifier M of metal or metal oxide, where Co exists mainly in non-crystal Co-B alloy or Co-M-B alloy and M is one of Sn, Fe, Zn, Cu and Co. The weight ratio among Co, M and B is 1 to 0-1.14 to 0.08-0.19. The catalyst is prepared through reducing Co ion and M oxide with BH4 ion and subsequent removal of impurity ion. The catalyst is used in hydrogenating crotonaldehyde into crotyl alcohol and has simple operation and high hydrogenating activity.

Description

Crotonic aldehyde amorphous hydrogenating catalyst containing cobalt and boron and preparation method thereof
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of new amorphous state Catalysts and its preparation method that crotonic aldehyde is selected hydrogenation processed fructus crotonis alcohol that is used for.
Background technology
It is important source material and the intermediate that spices, medicine and other fine chemical products are produced that α, beta-unsaturated aldehyde select hydrogenation to generate unsaturated alcohol, also is widely used in organic synthesis.Crotyl alcohol is a compound representative in the unsaturated alcohol.It is a kind of intermediate of very important organic synthesis, also can be used for weedicide simultaneously and is used as soil fumigant etc.So selecting shortening to generate the crotyl alcohol process, crotonic aldehyde has economic worth.
Crotonic aldehyde is a polyfunctional compound, and its existing C=C key has the C=O key again.Usually the method that obtains unsaturated alcohol is with tetrahydro-lithium aluminium, sodium borohydride or aluminum isopropylate reduction, but also needs strict control reaction conditions.If reagent is excessive or reaction temperature is higher, then carbon-to-carbon double bond and carbonyl are reduced simultaneously.No doubt can obtain the unsaturated alcohol of high yield with tetrahydro-lithium aluminium, sodium borohydride or aluminum isopropylate reductive method, but the separation difficulty of product and reductive agent, solvent etc., the aftertreatment of product is trouble, and the refuse of generation is also just a lot, causes environmental pollution easily.If adopt the method for catalysis of solid catalyst hydrogenation then can greatly reduce the generation of these refuses, product is easy to separate with catalyzer, and solvent only needs distillation simply or underpressure distillation to separate and can separate with reaction product, can greatly reduce reaction cost.Obtained extensive studies based on the catalyzer of precious metal (Pt, Ru, Pd) recent years, though it is active and selectivity is very high, costs an arm and a leg, and is not suitable for large-scale commercial production.Therefore must a kind of effective cheap catalyst of design.Nitta etc. find the Co catalyzer to α, and the beta-unsaturated aldehyde hydrogenation generates unsaturated alcohol and has very high selectivity.On the other hand, nanometer amorphous alloy has highly selective and high reactivity because the surface has property, the undersaturated active sites of coordination such as a large amount of chemistry to catalyzed reaction; Nano level particle diameter has been got rid of the influence of internal diffusion well, and the catalytic efficiency height is expected to replace traditional commercial catalysts.
Summary of the invention
The objective of the invention is to propose the novel amorphous alloy catalyst that crotonic aldehyde is selected hydrogenation crotyl alcohol preparation that is used for of a kind of catalytic efficiency height, good reaction selectivity, and propose this Preparation of catalysts method.
The catalyzer that is used for crotonic aldehyde selection hydrogenation processed fructus crotonis alcohol provided by the invention is a kind of amorphous alloy catalyst that contains cobalt and boron, and it is made up of cobalt, boron, metal additive M.Catalyst activity component and modifier calculate with the weight of wherein metallic element and are 1 with the weight of Co, and then the weight proportion of each component is in the catalyzer: the consumption of cobalt is 1, and the consumption of boron is 0.08～0.19, the consumption 0～1.14 of M; Wherein cobalt mainly exists with the form of Co-B or Co-M-B amorphous alloy, and metal additive M is meant that corresponding ion can be by BH 4 -A kind of in the ion reductive metal.
Catalyzer provided by the invention, in the described Co-M-B amorphous alloy, (Co+M) atomic ratio with boron is 1.5-4.0.
Catalyzer provided by the invention can adopt following two kinds of methods preparation:
First kind of method preparation of adopting chemical mixing and chemical reduction, second kind is adopted the decomposite two step method preparation of chemical reduction.
The method of first kind of chemical mixing and chemical reduction is specially in-10 ℃ to 40 ℃ temperature range, preferred 0 ℃ to 20 ℃, will contain Co ion and M ionic mixed aqueous solution under constant temperature stirs, with BH 4 -The reduction of the ionic aqueous solution.Particularly be that the dropping volumetric molar concentration is 0.2～2.0 the KBH that contains 4The aqueous solution, dropwise and continue to stir till no longer emitting bubble.The precipitation centrifuge washing of gained gets final product.KBH 4(Co+M): B=1 in the reduction step: 4 (mol ratios).
Second kind of decomposite two step method of chemical reduction is specially and at first adopts chemical reduction method to make the Co-B amorphous catalyst, then the Co-B amorphous catalyst that makes sneaked into the ethanolic soln that contains M salt of different concns.
Described when the preparation amorphous catalyst, by KBH 4Reductive contains cobalt ion (Co 2+), in the M ionic mixing solutions, cobalt ion, M ionic volumetric molar concentration are respectively 0.4～1,0～0.6.The volumetric molar concentration that contains the ethanolic soln of M salt in the decomposite two step method of described chemical reduction is 0～0.04, M: Co=0.5～20mol.%
Co of the present invention 2+The ionic precursor is selected from CoCl 2, BH 4 -The ionic precursor is selected from POTASSIUM BOROHYDRIDE.Described metal additive M is that its corresponding salt can be contained BH 4 -A kind of in the ion solution reductive metallic element, one or more in the preferred elements periodictable in group vib, VIIB family, group VIII, the IVA family metal.Metal additive commonly used is a kind of among Sn, Zn, Cu, Fe, the Co; Described M ionic precursor is the M positively charged ion, and when being Sn, Cu, Fe as M, described M ionic precursor is SnCl 2, SnCl 4, CuCl 2, FeCl 3
According to catalyzer provided by the invention, the active ingredient cobalt all exists with the non-crystalline state form, and in first method, metal additive M and Co-B form amorphous alloy, form with the Co-M-B amorphous alloy exists, or metal additive exists with oxide form separately.At this moment, ° locate a broad diffraction peak (as shown in Figure 1) in 2 θ=45 on the X-ray diffraction spectrogram of measuring with CuK α target, be the characteristic diffraction peak of cobalt series non-crystalline state alloy.
Activity of such catalysts provided by the invention can be tested with the following method:
Intermittently investigate catalyst activity in the tank reactor at the 0.22L stainless steel.Crotonic aldehyde, a certain amount of ethanol, catalyzer are put into still.Autoclave sealing back is with hydrogen exchange 3 times, to remove the air in the still.Preliminary filling hydrogen post-heating constant hydrogen after the temperature of reaction presses off the beginning reaction, and temperature of reaction is 50～200 ℃, and more excellent 80～120 ℃, hydrogen pressure 0.5～5MPa, more excellent 1～3MPa, stir speed (S.S.) is greater than 1000 rev/mins.Take out response sample at interval with gas chromatographic analysis crotyl alcohol content, crotonic aldehyde content and other possible product content wherein with certain hour in the reaction process.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of catalyzer
Embodiment
Further describe the present invention below by specific embodiment.
Embodiment 1: the preparation of ultra-fine Co-B amorphous alloy catalyst
The freshly prepared 2.00 M POTASSIUM BOROHYDRIDE aqueous solution were at the uniform velocity splashed into cobalt chloride (CoCl for 13 milliliters in 10 minutes 26H 2O, in aqueous solution 1.0M), mol ratio is B/Co=4/1.Reaction soln places water bath with thermostatic control and in addition violent induction stirring, gained black precipitate centrifugation is washed till neutrality with distilled water, again promptly can be used for active testing behind the absolute ethanol washing, catalyzer is designated as CoB, and the part characterization result of this catalyzer is shown in table one.
Embodiment 2: ultra-fine CoSn IIB, CoSn IVThe preparation of B amorphous alloy catalyst
Catalyzer adopts the method preparation of chemical mixing and chemical reduction.The freshly prepared 2.00M POTASSIUM BOROHYDRIDE aqueous solution is splashed into cobalt chloride (CoCl 26H 2O, 1.0M) and tin protochloride (SnCl 22H 2O) or tin chloride (SnCl 45H 2O) in the mixed aqueous solution.Keep cobalt chloride (CoCl 26H 2O, adding volume 1.0M) can obtain the different catalyzer of tin content by the add-on that changes tin protochloride or tin chloride solution.Mol ratio is fixed as B/ (Co+Sn)=4/1 during reduction.Reaction soln places water bath with thermostatic control and in addition violent induction stirring.Gained black precipitate centrifugation is washed till neutrality with distilled water, and promptly can be used for active testing behind the absolute ethanol washing, catalyzer is designated as CoSn again IIB1, CoSn IIB2, CoSn IIB3, CoSn IVB1, CoSn IVB2, CoSn IVB3.The part characterization result of this catalyzer is shown in table one.
The catalyzer that Zn and Cu modify adopts above-mentioned same method preparation, and zinc salt and mantoquita are dissolved in the mixed solution respectively in advance.Catalyzer is designated as CoZnB1, CoZnB2, CoZnB3, CoZnB4, CoCuB1, CoCuB2, CoCuB3.The part characterization result of this catalyzer is shown in table two, table three.
Embodiment 3: the preparation of ultra-fine CoFeB amorphous alloy catalyst
Catalyzer adopts the method preparation of chemical mixing and chemical reduction.The freshly prepared 2.00M POTASSIUM BOROHYDRIDE aqueous solution is splashed into cobalt chloride (CoCl 26H 2O) and iron(ic) chloride (FeCl 36H 2O) in the mixed aqueous solution, wherein keep adding cobalt chloride (CoCl 26H 2O) and iron(ic) chloride (FeCl 36H 2O) total mole number is 0.01.Can obtain cobalt, the different catalyzer of iron level by changing the mol ratio that adds cobalt chloride and ferric chloride Solution.Mol ratio is fixed as B/ (Co+Fe)=4/1 during reduction.Reaction soln places water bath with thermostatic control and in addition violent induction stirring.Gained black precipitate centrifugation is washed till neutrality with distilled water, and promptly can be used for active testing behind the absolute ethanol washing, catalyzer is designated as CoFeB1, CoFeB2, CoFeB3 again, and the part characterization result of this catalyzer is shown in table four.
Embodiment 4: ultra-fine CoB-Sn IIAnd CoB-Sn IvThe preparation of amorphous alloy catalyst
Catalyzer adopts the decomposite two step method preparation of chemical reduction.At first adopt chemical reduction method to make the Co-B amorphous catalyst, then the Co-B amorphous catalyst that makes is sneaked into the 45ml tin protochloride (SnCl of different concns 22H 2O) or tin chloride (SnCl 45H 2O) ethanolic soln.
The catalyzer that Fe, Zn, Cu, Co modify adopts above-mentioned same method preparation.The Co-B amorphous catalyst that makes is sneaked into the 45ml iron(ic) chloride (FeCl of different concns 36H 2O), zinc chloride (ZnCl 2), cupric chloride (CuCl 22H 2O) or cobalt chloride (CoCl 26H 2O) ethanolic soln.
Crotonic aldehyde hydrogenation activity test: ultra-fine CoB, Co-M-B, CoB-M (M=Sn, Fe, Zn, Cu, Co) amorphous alloy
Catalyst levels is 0.5 gram, 5 milliliters of crotonic aldehydes, and 45 milliliters of 99.5% ethanol, 100 ℃ of temperature of reaction, hydrogen pressure 1.0MPa, 1000 rev/mins of stir speed (S.S.)s, hydrogenation the results are shown in table five～table ten one.
Table one, non-crystalline state CoB, CoSn IIB, CoSn IVThe specific surface area of B catalyst series and body phase composite
Specific surface area of catalyst (m 2G -1) body phase composite (atomic ratio)
CoB 17.8 Co 65.6B 34.4
CoSn IIB1 21.2 Co 61.8Sn 0.7B 37.5
CoSn IIB2 32.8 Co 62.6Sn 1.2B 36.2
CoSn IIB3 66.3 Co 61.7Sn 3.1B 35.2
CoSn IVB1 37.6 Co 63.0Sn 0.6B 36.4
CoSn IVB2 54.4 Co 62.1Sn 1.3B 36.6
CoSn IVB3 76.8 Co 62.6Sn 2.6B 34.8
The specific surface area of table two, non-crystalline state CoZnB catalyst series and body phase composite
Specific surface area of catalyst (m 2G -1) body phase composite (atomic ratio)
CoZnB1 26.2 Co 66.7Zn 0.7B 32.6
CoZnB2 67.3 Co 67.0Zn 1.2B 31.8
CoZnB3 79.8 Co 65.4Zn 2.8B 31.8
CoZnB4 88.9 Co 65.8Zn 4.8B 29.4
The specific surface area of table three, non-crystalline state CoCuB catalyst series and body phase composite
Specific surface area of catalyst (m 2G -1) body phase composite (atomic ratio)
CoCuB1 35.8 Co 66.8Cu 1.3B 34.4
CoCuB2 66.8 Co 65.3Cu 2.7B 32.1
CoCuB3 74.3 Co 64.9Cu 0.8B 34.3
The specific surface area of table four, amorphous CoFeB catalyst series and body phase composite
Specific surface area of catalyst (m 2G -1) body phase composite (atomic ratio)
CoFeB1 27.4 Co 54.2Fe 13.6B 32.2
CoFeB2 32.5 Co 43.8Fe 24.9B 31.3
CoFeB3 35.4 Co 30.8Fe 37.1B 32.1
Table five, non-crystalline state CoB, CoSn IIB, CoSn IVThe crotonic aldehyde hydrogenation activity of B, CoFeB catalyst series
Catalyzer aTransformation efficiency (%) bSelectivity (%)
CoB 89.3 20.2
CoSn IIB1 84.1 20.1
CoSn IIB2 80.3 22.1
CoSn IIB3 63.9 17.4
CoSn IVB1 99.5 17.2
CoSn IVB2 98.9 16.8
CoSn IVB3 93.8 13.6
CoZnB1 77.5 19.1
CoZnB2 60.6 27.3
CoZnB3 59.4 19.5
CoZnB4 40.6 17.8
CoCuB1 84.5 22.1
CoCuB2 84.2 19.5
CoCuB3 70.2 17.3
CoFeB1 72.3 34.6
CoFeB2 64.5 40.7
CoFeB3 24.4 67.1
Table six, xmol.%Co IB-Sn IIThe crotonic aldehyde hydrogenation activity of catalyst series
The add-on of additive aTransformation efficiency (%) bSelectivity (%)
1 86.6 38.2
2 80.4 43.7
5 70.3 39.9
10 41.2 16.8
Table seven, xmol.%CoB-Sn IVThe crotonic aldehyde hydrogenation activity of catalyst series
The add-on of additive aTransformation efficiency (%) bSelectivity (%)
0.5 90.9 37.1
1 82.5 43.7
2 79.9 45.6
5 44.4 34.1
The crotonic aldehyde hydrogenation activity of table eight, xmol.%CoB-Zn catalyst series
The add-on of additive aTransformation efficiency (%) bSelectivity (%)
1 90.9 30.6
2 89.2 30.9
5 70.8 38.8
10 70.3 43.5
20 56.2 36.2
The crotonic aldehyde hydrogenation activity of table nine, xmol.%CoB-Cu catalyst series
The add-on of additive aTransformation efficiency (%) bSelectivity (%)
1 55.9 33.6
2 46.6 37.4
5 39.6 34.0
The crotonic aldehyde hydrogenation activity of table ten, xmol.%CoB-Fe catalyst series
The add-on of additive aTransformation efficiency (%) bSelectivity (%)
1 64.0 39.8
2 56.4 44.5
5 61.9 53.9
10 35.1 51.6
The crotonic aldehyde hydrogenation activity of table ten one, xmol.%CoB-Co catalyst series
The add-on of additive aTransformation efficiency (%) bSelectivity (%)
1 51.6 34.7
2 42.0 41.2
5 41.3 45.1
10 30.2 30.6
aThe transformation efficiency of 2h crotonic aldehyde
bThe pairing selectivity of the highest yield of crotyl alcohol

Claims (8)

1. one kind is used for the amorphous alloy catalyst that contains cobalt and boron that crotonic aldehyde is selected hydrogenation processed fructus crotonis alcohol, it is characterized in that it is made up of cobalt, boron, additive metal M; Catalyst activity component and modifier calculate with the weight of wherein metallic element, and are 1 with the weight of cobalt, and then the weight ratio of each component is in the catalyzer: the consumption of cobalt is 1, and boron is 0.08～0.19, and M is 0～1.14; Wherein cobalt mainly exists with the form of Co-B or Co-M-B amorphous alloy, and metal additive M can be by BH for its ion 4 -A kind of in the ion reductive metal.
2. catalyzer according to claim 1 is characterized in that in the described Co-M-B amorphous alloy, and (Co+M) atomic ratio with boron is 1.5～4.0.
3. catalyzer according to claim 1 is characterized in that metal additive M is selected from one or more in group vib, VIIB family, group VIII, the IVA family metal in the periodic table of elements.
4. according to the described catalyzer of claim 3, it is characterized in that metal additive M is selected from a kind of among Sn, Fe, Zn, Cu, the Co.
5. one kind as claimed in claim 1ly is used for the preparation method that crotonic aldehyde is selected the amorphous catalyst of hydrogenation processed fructus crotonis alcohol, it is characterized in that adopting chemical mixing and chemical reduction method, concrete steps are as follows: in-10 ℃ to 40 ℃ temperature range, will contain Co ion and M ionic mixed aqueous solution under constant temperature stirs to contain BH 4 -The reduction of the ionic aqueous solution.
6. one kind as claimed in claim 1ly is used for the preparation method that crotonic aldehyde is selected the amorphous catalyst of hydrogenation processed fructus crotonis alcohol, it is characterized in that adopting the decomposite two step method of chemical reduction, concrete steps are as follows: at first adopt chemical reduction method to make the Co-B amorphous catalyst, then the Co-B amorphous catalyst that makes is sneaked into the ethanolic soln that contains M salt of different concns.
7. according to claim 5 or 6 described Preparation of catalysts methods, it is characterized in that metal additive adopts a kind of among Sn, Fe, Zn, Cu, the Co.
8. Preparation of catalysts method according to claim 7 is characterized in that described Co 2+The ionic precursor is selected from CoCl 2, Sn ionic precursor is selected from SnCl 2, SnCl 4, Fe ionic precursor is selected from FeCl 3, Zn ionic precursor is selected from ZnCl 2, Cu ionic precursor is selected from CuCl 2, BH 4 -The ionic precursor is selected from POTASSIUM BOROHYDRIDE.
CNB2003101084379A 2003-11-06 2003-11-06 Amorphous catalyst with cobalt and boron for crotonaldehyde hydrogenation and preparation thereof Expired - Fee Related CN100475334C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702971A (en) * 2016-01-27 2016-06-22 西安科技大学 Core-shell gold@ cobalt-boron catalyst for fuel cell
CN109160892A (en) * 2018-10-15 2019-01-08 禄丰天宝磷化工有限公司 A kind of method that catalytic hydrogenation prepares 3 methylthiol propyl alcohol
CN109499574A (en) * 2018-12-10 2019-03-22 怀化学院 Amorphous alloy catalyst and preparation method thereof
CN109499575A (en) * 2018-12-10 2019-03-22 怀化学院 Application of the amorphous alloy catalyst in selective hydrogenation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702971A (en) * 2016-01-27 2016-06-22 西安科技大学 Core-shell gold@ cobalt-boron catalyst for fuel cell
CN105702971B (en) * 2016-01-27 2018-01-12 西安科技大学 A kind of hud typed golden@cobalts B catalyst of fuel cell
CN109160892A (en) * 2018-10-15 2019-01-08 禄丰天宝磷化工有限公司 A kind of method that catalytic hydrogenation prepares 3 methylthiol propyl alcohol
CN109160892B (en) * 2018-10-15 2020-09-22 天宝动物营养科技股份有限公司 Method for preparing 3-methylthio propanol by catalytic hydrogenation
CN109499574A (en) * 2018-12-10 2019-03-22 怀化学院 Amorphous alloy catalyst and preparation method thereof
CN109499575A (en) * 2018-12-10 2019-03-22 怀化学院 Application of the amorphous alloy catalyst in selective hydrogenation

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