CN1837396A - Quaternary amorphous alloy, its preparation method and application - Google Patents

Quaternary amorphous alloy, its preparation method and application Download PDF

Info

Publication number
CN1837396A
CN1837396A CNA2006100259045A CN200610025904A CN1837396A CN 1837396 A CN1837396 A CN 1837396A CN A2006100259045 A CNA2006100259045 A CN A2006100259045A CN 200610025904 A CN200610025904 A CN 200610025904A CN 1837396 A CN1837396 A CN 1837396A
Authority
CN
China
Prior art keywords
amorphous alloy
quaternary
preparation
solution
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2006100259045A
Other languages
Chinese (zh)
Inventor
李和兴
李辉
杨平锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Normal University
University of Shanghai for Science and Technology
Original Assignee
Shanghai Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Normal University filed Critical Shanghai Normal University
Priority to CNA2006100259045A priority Critical patent/CN1837396A/en
Publication of CN1837396A publication Critical patent/CN1837396A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This invention provides a quaternary amorphous alloy (M1-M2-N1-N2) and a method for preparing it and its application in hydrogenation of liquid maltose. Its bulk phase comprises two metals and two metalloids, and it is spherical particle with 5-100nm grain size. The method for preparation of it is as follows: mixing fully a metal salt solution and a reducer solution; adding slowly another reducer solution for reduction; centrifugalizing the black solid obtained from the reaction, washing it with deionized water until it becomes neutral to get M1-M2-N1-N2. It can be used as catalysts for hydrogenation of unsaturated function group compounds, the performance of hydrogenation of liquid maltose to produce maltose alcohol is better than that of binary and alloy amorphous alloy obtained with general reduction, and is much better than that of Raney Ni skeleton catalyst generally used in hydrogenation of liquid maltose.

Description

Quaternary amorphous alloy and its production and application
Technical field
The invention belongs to chemical technology field, relate to a kind of quaternary amorphous alloy and preparation method thereof, and be applied to show in the liquid phase hydrogenation of maltose excellent hydrogenation performance.
Technical background
Industrial, maltose alcohol mainly is to make by the liquid phase hydrogenation of maltose, the external corporate boss who produces maltose alcohol will concentrate on Europe, the United States and Japan, all adopting skeleton Raney Ni is catalyzer, but mainly there is following defective: need to carry out alkali in (1) Raney Ni catalyst preparation process and filter, produce serious environmental pollution; (2) Raney Ni catalyzer bad mechanical strength is pulverized in the use easily, not only causes catalyst deactivation, and fragment also can stop up reactor, and simultaneously, part Ni is mingled in the product, and HUMAN HEALTH is constituted harm; (3) Raney Ni catalysis hydrogenation of maltose generally need carry out under 100～150 ℃ and 4.0-8.0MPa, because maltose is to be formed by two glucose molecule condensations, High Temperature High Pressure will cause disaccharide to transform to monose, produce by product, often obtain the mixture of multi-sugar alcohol, the content of maltose alcohol generally about 70%, influences the purity of maltose alcohol product.Amorphous alloy is the unordered and new catalytic material of short range order of a class long-range, its particular structure feature is given its excellent catalytic activity, selectivity, the anti-poisoning and corrosion resistance nature, also have eco-friendly characteristics simultaneously, become the efficient and environmental friendliness new catalytic material of tool DEVELOPMENT PROSPECT of 21st century.
At present generally adopt chemical reduction method to prepare amorphous alloy catalyst, preparation mostly be binary or ternary amorphous alloy catalyst.In Journal of Catalysis 150,434～438,1994, once reported KBH with 2.5M 4The aqueous solution is at 25 ℃, be added drop-wise in the 0.1M nickel acetate ethanolic soln under stirring, with ammoniacal liquor and a large amount of distilled water wash precipitation of 6 milliliters of 8M, obtain a kind of non-crystalline state Ni-B Ultra-fine Particle Catalysts successively, this method has become the ordinary method of preparation M-B amorphous alloy catalyst.Journal ofMolecular Catalysis A:Chemical 152,213-223 once reported the NaBH with 0.1M in 2000 4The aqueous solution is at 30 ℃, be added drop-wise in the 0.1M nickel acetate aqueous solution under stirring, with a large amount of distilled water and washing with alcohol precipitation, obtain a kind of non-crystalline state Ni-P-B Ultra-fine Particle Catalysts successively, this method has become the common method of preparation ternary amorphous alloy catalyst.
Summary of the invention
The object of the present invention is to provide a kind of preparation quaternary amorphous alloy (M 1-M 2-N 1-N 2) catalyzer;
Another object of the present invention is to provide the method for this quaternary amorphous alloy;
A further object of the present invention provides and this catalyzer is applied to the liquid phase hydrogenation of maltose prepares maltose alcohol, for industrial liquid phase hydrogenation of maltose finds efficient, eco-friendly catalyzer.
Goal of the invention of the present invention is achieved by the following technical solution:
A kind of quaternary amorphous alloy (M 1-M 2-N 1-N 2), its body is made up of two kinds of metals and two kind metals, is spherical particle, and particle diameter is in the scope of 5～100nm.Described two kinds of metal (M 1And M 2) be selected from the inorganic salt of nickel, cobalt, palladium, ruthenium, platinum.Described two kinds of metalloid (N 1And N 2) be selected from hypophosphite or its mixture and hydroborate or its mixture.
The preparation method of this quaternary amorphous alloy comprises the steps:
A, be dissolved in two kinds of metal inorganic salts and reductive agent hypophosphite in the deionized water respectively, thorough mixing is made into clear solution, drip another kind of borane reducing agent hydride solution, temperature of reaction is 0～90 ℃, and their mol ratio is: two kinds of metal inorganic salt/hypophosphite/hydroborate=1: 2～10: 2～10.
C, above-mentioned solution fully stirred with magnetic agitation carry out reduction reaction;
D, the black solid that obtains wash to neutral with the deionized water centrifugation, make the amorphous alloy of quaternary.
Wherein the reductive agent hypophosphite described in the A step is selected from inferior sodium phosphate, ortho phosphorous acid potassium or its mixture;
Wherein the borane reducing agent hydride described in the A step is selected from sodium borohydride, POTASSIUM BOROHYDRIDE or its mixture.
Prepared quaternary amorphous alloy catalyzer is applied to the liquid phase hydrogenation of maltose.
Quaternary amorphous alloy provided by the invention obtains being higher than the skeleton Raney Ni catalyzer of industrial application as the hydrogenation catalyst of liquid phase maltose, and the binary for preparing far above the conventional chemical reduction method or the hydrogenation performance of ternary amorphous alloy.
Different catalysts provided by the invention adopts the high-pressure liquid phase hydrogenation reaction to investigate it produces maltose alcohol at hydrogenation of maltose catalytic activity.Concrete steps are: in the 200ml autoclave, add a certain amount of catalyzer successively, and the maltose solution of 50ml 50% (w/w), airtight back with the air in the 3.0MPa hydrogen exchange still, 4～5 times repeatedly.Charge into 3.0MPa hydrogen then, close needle-valve, heated constant temperature is in 100 ℃ of needed temperature of reaction.Pressure in the heat-processed mesohigh still rises gradually, opens magnetic stirring apparatus after reaching balance, and this moment, hydrogenation reaction began.For eliminating the influence of diffusional effect to reaction kinetics, the control stirring velocity is 1000rpm.Hydrogen pressure in the observing response process and is converted to hydrogen-absorption speed (R over time m).Reaction product detects with the liquid chromatography (Agrlent 1100 Series) of being furnished with CARBOsep COREGEL 87C chromatographic column and differential refraction detector.Column temperature: 80 ℃; Moving phase: deionized water; Flow velocity: 0.6ml/min.Analytical results shows that maltose alcohol is unique product (all catalyzer are 100% to the selectivity of maltose alcohol) in detectability, and the mensuration of maltose transformation efficiency also obtains from the liquid chromatography data.Repeated experiments shows that all results are all in limit of error.
Product with the present invention's preparation carries out structural characterization by following means: the 18 kilovolts of amorphous structures that change target x-ray diffractometer (XRD) working sample of D/max-rB type that adopt Japanese company of science to produce; Utilize the shape and size of JEM-2010 transmission electron microscope (TEM) the direct viewing product that Japanese JEOL company produces.
Description of drawings
Fig. 1 is the XRD spectra of product quaternary amorphous alloy of the present invention;
Fig. 2 is the TEM photo of product quaternary amorphous alloy of the present invention.
Embodiment
Further specify the present invention below in conjunction with specific embodiment and how to realize that the following examples will give further instruction to the present invention, but (agents useful for same is a chemical pure among the embodiment) not thereby limiting the invention:
Embodiment 1:
Step 1: with a certain amount of CoCl 2, NiCl 2And NaH 2PO 2(being solid) is dissolved in respectively in the deionized water, is made into the clear solution of 0.86M.Take by weighing a certain amount of KBH 4(solid) and NaOH are dissolved in the clear solution that is made into 2.0M in the deionized water together with it, and be standby.
Step 2: measure above-mentioned CoCl according to a certain percentage respectively 2, NiCl 2And NaH 2PO 2Solution 12mL, 8mL and 40mL mix fully, and constant temperature water bath to 30 ℃ is then at the KBH of step 1 preparation of above-mentioned mixed solution and dripping 34mL 4Solution, and fully stir with magnetic stirring apparatus, gradual slow generates black particle in the solution, and has gas to emerge, and drips off KBH 4Continue to stir 15min behind the solution.Material molar ratio: Co 2++ Ni 2+/ H 2PO 2 -/ BH 4 -=1: 2: 4.
Step 3: the black particle that makes is extremely neutral with deionized water centrifugation washing, obtain quaternary amorphous alloy (Ni-Co-P-B-2) catalyzer.
Step 4: the catalyzer that step 3 is obtained is used for the liquid phase hydrogenation of maltose.
As shown in Figure 1, can determine that from the disperse peak shape of its about 45 ° of positions the sample that makes is a non-crystalline state.All alloy samples that make with method provided by the present invention are non-crystalline state.As shown in Figure 2, the sample that as seen makes with method provided by the present invention from photo is a spheroidal particle.
Embodiment 2:
Step 1: with step 1 among the embodiment 1
Step 2: measure above-mentioned CoCl according to a certain percentage respectively 2, NiCl 2And NaH 2PO 2Solution 10mL, 10mL and 40mL, remaining step is with step 2 among the embodiment 1.
Step 3:, obtain quaternary amorphous alloy (Ni-Co-P-B-1) catalyzer with step 3 among the embodiment 1.
Step 4: with embodiment 1 step 4.
Embodiment 3:
Step 1: with step 1 among the embodiment 1
Step 2: measure above-mentioned CoCl according to a certain percentage respectively 2, NiCl 2And NaH 2PO 2Solution 14mL, 6mL and 40mL, remaining step is with embodiment 1.
Step 3:, obtain quaternary amorphous alloy (Ni-Co-P-B-3) catalyzer with step 3 among the embodiment 1.
Step 4: with embodiment 1 step 4.
Embodiment 4:
Step 1: with a certain amount of CoCl 2And NaH 2PO 2Be dissolved in respectively in the deionized water, be made into the clear solution of 0.85M, take by weighing a certain amount of KBH 4(solid) and NaOH are dissolved in the clear solution that is made into 2.0M in the deionized water together with it, and be standby.
Step 2: measure above-mentioned CoCl respectively 2And NaH 2PO 2Solution 20mL and 40mL stir thorough mixing, and constant temperature water bath to 70 ℃ is then at the KBH of step 1 preparation of above-mentioned mixed solution and dripping 34mL 4Solution, and fully stir with magnetic stirring apparatus, gradual slow generates black particle in the solution, and has gas to emerge, and drips off KBH 4Continue to stir 15min behind the solution.Material molar ratio: Co 2+/ H 2PO 2 -/ BH 4 -=1: 2: 4.
Step 3: the black particle that makes is extremely neutral with deionized water centrifugation washing, obtain ternary amorphous alloy (Co-P-B) catalyzer.
Step 4: with step 4 among the embodiment 1.
Embodiment 5:
Step 1: with a certain amount of NiCl 2And NaH 2PO 2Be dissolved in respectively in the deionized water, be made into the clear solution of 0.85M, take by weighing a certain amount of KBH 4(solid) and NaOH are dissolved in the clear solution that is made into 2.0M in the deionized water together with it, and be standby.
Step 2: measure above-mentioned NiCl respectively 2And NaH 2PO 2Solution 20mL and 40mL stir thorough mixing, and constant temperature water bath to 70 ℃ is then at the KBH of step 1 preparation of above-mentioned mixed solution and dripping 34mL 4Solution, and fully stir with magnetic stirring apparatus, gradual slow generates black particle in the solution, and has gas to emerge, and drips off KBH 4Continue to stir 15min behind the solution.Material molar ratio: Ni 2+/ H 2PO 2 -/ BH 4 -=1: 2: 4.
Step 3: the black particle that makes is extremely neutral with deionized water centrifugation washing, obtain ternary amorphous alloy (Ni-P-B) catalyzer.
Step 4: with step 4 among the embodiment 1.
Embodiment 6:
Step 1: the 0.85M CoCl of measuring step 1 preparation among the embodiment 1 2Solution 20mL under the ice-water bath condition, drips the KBH of step 1 preparation among the embodiment 1 4Solution 34mL, and fully stir with magnetic stirring apparatus, gradual slow generates black particle in the solution, and has gas to emerge, and drips off KBH 4Continue to stir 15min behind the solution.Material molar ratio: Co 2+/ BH 4 -=1: 4.
Step 2: the black particle that makes is extremely neutral with deionized water centrifugation washing, obtain binary amorphous alloy (Co-B) catalyzer.
Step 3: with step 4 among the embodiment 1.
Embodiment 7:
Step 1: the 0.85M NiCl of measuring step 1 preparation among the embodiment 1 2Solution 20mL, remaining step is with step 1 among the embodiment 6.Material molar ratio: Ni 2+/ BH 4 -=1: 4.
Step 2: the black particle that makes is extremely neutral with deionized water centrifugation washing, obtain binary amorphous alloy (Ni-B) catalyzer.
Step 3: with step 4 among the embodiment 1.
Embodiment 8:
Step 1: take by weighing 80-100 purpose Ni-Al alloy 3.0g, under the normal temperature, slowly (about 25min) is added to 20mL, among the 6.0M NaOH, slowly stirs simultaneously, under 90 ℃ of oil bath heating, fully stirs extracting 3.0h at last.
Step 2: the precipitate with deionized water washing that step 1 among the embodiment 8 makes is extremely neutral, obtain skeleton Raney Ni catalyzer, and be kept in the deionized water standby.
Step 3: with step 4 among the embodiment 1.
The table 1 that the results are shown in to last step of the foregoing description 1-8.
The various character of table 1 different catalysts and catalytic performance thereof are relatively a
Catalyzer Body phase composite (atom%) Sact (m 2/g metal) R m (mmol/h .g meata) R s (mmol/h. m 2) Transformation efficiency (%)
Ni-B Co-B Ni-P-B Co-P-B Ni-Co-P-B-1 Ni-Co-P-B-2 Ni-Co-P-B-3 Raney Ni b Ni 75.0B 25.0 Co 76.0B 24.0 Ni 75.0P 10.5B 15.5 Co 76.1P 6.4B 17.5 Ni 34.9Co 35.3P 11.7B 18.1 Ni 27.7Co 42.1P 11.6B 18.6 Ni 20.8Co 49.2P 11.8B 18.2 Ni 9.5 10.9 10.8 12.1 15.0 17.8 15.8 46.0 8.21 8.83 31.0 22.6 65.7 83.4 69.6 7.5 0.88 0.81 2.87 1.87 4.38 4.70 4.40 0.20 25.1 19.6 51.2 43.8 77.8 93.1 80.0 10.5
aReaction conditions: 1.0g catalyzer, 50mL 40wt.% maltose solution, T=373K, P H2=3.0MPa, reaction times=2h, stir speed (S.S.)=1200rpm; The selectivity of b maltose alcohol is 73%.
Result from table, as can be seen at T=373K, P H2=3.0MPa, under the condition of reaction times=2h, quaternary amorphous alloy (Ni-Co-P-B) catalyzer is used for the liquid phase hydrogenation of maltose, show good hydrogenation performance, its selectivity～100, transformation efficiency is 93.1%, apparently higher than the hydrogenation performance of binary amorphous alloy, ternary amorphous alloy, and farther hydrogenation performance far above Raney Ni.

Claims (7)

1, a kind of quaternary amorphous alloy, its body is made up of two kinds of metals and two kind metals, is spherical particle, and particle diameter is in the scope of 5～100nm.
2, quaternary amorphous alloy according to claim 1 is characterized in that: described two kinds of metals are selected from the inorganic salt of nickel, cobalt, palladium, ruthenium, platinum.
3, quaternary amorphous alloy according to claim 1 is characterized in that: described two kinds of metalloids are selected from hypophosphite or its mixture and hydroborate or its mixture.
4, the preparation method of claim 1,2 or 3 described a kind of quaternary amorphous alloys comprises the steps:
A, be dissolved in two kinds of metal inorganic salts and reductive agent hypophosphite in the deionized water respectively, thorough mixing is made into clear solution, drip another kind of borane reducing agent hydride solution, temperature of reaction is 0～90 ℃, and their mol ratio is: two kinds of metal inorganic salt/hypophosphite/hydroborate=1: 2～10: 2～10.
C, above-mentioned solution fully stirred with magnetic agitation carry out reduction reaction;
D, the black solid that obtains wash to neutral with the deionized water centrifugation, make the amorphous alloy of quaternary.
5, the preparation method of a kind of quaternary amorphous alloy according to claim 4 is characterized in that: the reductive agent hypophosphite described in the A step is selected from inferior sodium phosphate, ortho phosphorous acid potassium or its mixture.
6, the preparation method of a kind of quaternary amorphous alloy according to claim 4 is characterized in that: the borane reducing agent hydride described in the A step is selected from sodium borohydride, POTASSIUM BOROHYDRIDE or its mixture.
7, the purposes of claim 1,2 or 3 described a kind of quaternary amorphous alloys, it is characterized in that: described quaternary amorphous alloy is applied to the liquid phase hydrogenation of maltose as catalyzer.
CNA2006100259045A 2006-04-21 2006-04-21 Quaternary amorphous alloy, its preparation method and application Pending CN1837396A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2006100259045A CN1837396A (en) 2006-04-21 2006-04-21 Quaternary amorphous alloy, its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2006100259045A CN1837396A (en) 2006-04-21 2006-04-21 Quaternary amorphous alloy, its preparation method and application

Publications (1)

Publication Number Publication Date
CN1837396A true CN1837396A (en) 2006-09-27

Family

ID=37014903

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006100259045A Pending CN1837396A (en) 2006-04-21 2006-04-21 Quaternary amorphous alloy, its preparation method and application

Country Status (1)

Country Link
CN (1) CN1837396A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549384A (en) * 2014-12-23 2015-04-29 桂林电子科技大学 Preparation method of Ni-P-B nano-spherical alloy catalyst as well as application of catalyst
CN110694657A (en) * 2019-11-05 2020-01-17 宁夏大学 Simple high-carbon aldehyde synthesis catalyst
CN112774681A (en) * 2019-11-08 2021-05-11 国家能源投资集团有限责任公司 Amorphous alloy catalyst and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549384A (en) * 2014-12-23 2015-04-29 桂林电子科技大学 Preparation method of Ni-P-B nano-spherical alloy catalyst as well as application of catalyst
CN104549384B (en) * 2014-12-23 2020-03-10 桂林电子科技大学 Preparation method and application of Ni-P-B nanosphere alloy catalyst
CN110694657A (en) * 2019-11-05 2020-01-17 宁夏大学 Simple high-carbon aldehyde synthesis catalyst
CN112774681A (en) * 2019-11-08 2021-05-11 国家能源投资集团有限责任公司 Amorphous alloy catalyst and preparation method and application thereof
CN112774681B (en) * 2019-11-08 2024-07-05 国家能源投资集团有限责任公司 Amorphous alloy catalyst, and preparation method and application thereof

Similar Documents

Publication Publication Date Title
US10913052B1 (en) Supported bimetallic core-shell structure catalyst and its preparation method
CN1820850A (en) Non-crystalline alloy catalyst of uniform grain size and its preparing method
CN113522288B (en) Catalyst for catalyzing ammonia borane hydrolysis hydrogen production and preparation method and application thereof
CN102040203B (en) Preparation method and application of nano nickel phosphide
CN1850330A (en) Load-type non-crystal-state alloy hydogenation catalyst and preparing method
CN102500374B (en) Copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as preparation method and application thereof
CN1442260A (en) Method for preparing metal nano powder
CN101972651B (en) Metal palladium nano-material catalyst and preparation and application thereof
CN106622224B (en) Application of the nanometer Au-based catalyst in formic acid or formates synthesis
CN1837396A (en) Quaternary amorphous alloy, its preparation method and application
CN103638938A (en) Preparation method of catalyst for biological oil hydrodeoxygenation
CN101298102B (en) Preparation of nano cobalt granule
CN113814408B (en) Preparation and component regulation and control method of CuPd alloy nanocrystalline
CN106810419B (en) Graphene-loaded metal compound for preparing ethanol catalyst by acetic acid hydrogenation and preparation method thereof
Wang et al. Preparation of bimetallic CuxAgy nanoparticles and their catalytic performance in hydrogenation of 4-nitrophenol with H2 to 4-aminophenol
CN100391664C (en) Method for preparing single dispersion metal nanometer particles
CN101380577B (en) Hollow amorphous alloy nano-sphere catalyst, preparation method and use thereof
CN100471565C (en) Amorphous alloy catalyst for hydrogenation of maltose, its preparation and application
CN100357286C (en) Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol
CN1078095C (en) Amorphous alloy catalyst containing nickel and phosphorus and preparation method thereof
CN108465468A (en) A kind of preparation method of low carbon alcohol by synthetic gas catalyst
Gao et al. Synthesis of organobentonite-supported Pd composite catalyst used for the catalytic transfer hydrogenation of polyunsaturated fatty acid methyl ester
CN101543769B (en) Method for preparing amorphous alloy maltose catalyst and application thereof
CN101869838B (en) Nano catalyst for synthesizing glycol by hydrogenation of diester oxalate
CN101108344B (en) Amorphous ruthenium boron catalyzer with mesopore structure and method of manufacturing the same and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication