CN1304918A - Non-crystal catalyst for hydrogenating glucose and its preparing process - Google Patents
Non-crystal catalyst for hydrogenating glucose and its preparing process Download PDFInfo
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Abstract
A non-crystal catalyst for preparing sorbitol by hydrogenating glucose is prepared from Ni (Co), B, metal additive M and porous carrier through reduction reaction at 0-100 deg.c in solution containing BH4 ions, It has high hydrogenation activity.
Description
The invention belongs to chemical technology field, is the new amorphous state Catalysts and its preparation method that is used for glucose hydrogenation system sorbyl alcohol.
Sorbyl alcohol is used very extensive in industrial production and daily life, and it is synthesise vitamins C and the important source material of making explosive; Also as washing composition and the additive of ointment and the thickening material of paper and fiber; Also can be used as liquid medicine, directly take or do skin cream as syrup etc.; In addition, can also be used for synthetic resins, tensio-active agent and defoamer etc.And sorbyl alcohol is mainly by the glucose hydrogenation preparation, so glucose hydrogenation system sorbyl alcohol process has economic worth and social effect.
In existing glucose hydrogenation catalyzer, noble metal catalysts such as load type palladium, platinum, rhodium and ruthenium have very high glucose hydrogenation activity, but the cost height.Present industrial hydrogenating glucose to prepare sorbierite generally adopts RaneyNi to make catalyzer, and the subject matter of existence has: (1) environmental pollution is serious; (2) RaneyNi poor catalytic activity; (3) catalyzer mud and product separation difficulty.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.
The objective of the invention is to propose a kind of catalytic efficiency height, eco-friendlyly be used for novel nickeliferous (cobalt) and the amorphous alloy catalyst of boron that the glucose shortening prepares sorbyl alcohol, and propose this Preparation of catalysts method.
The catalyzer that is used for glucose hydrogenation system sorbyl alcohol provided by the invention is the amorphous alloy catalyst of a kind of nickeliferous (cobalt) and boron, it is made up of nickel (cobalt), boron, metal additive M and porous material carrier L, the weight proportion of each component is as follows: the consumption with nickel (cobalt) is 1, then the consumption of boron is 0.005～1.74, the consumption of M is 0～30, and the consumption of L is 0～42.Wherein, described nickel (cobalt) mainly exists with the form of Ni (Co)-B or Ni (Co)-M-B amorphous alloy; Described metal additive M refers to can be by BH
4 -Ion is reduced to the metal of simple substance attitude one or more from corresponding ion, exists with the form of Ni (Co)-M-B amorphous alloy; Nickel (cobalt) is 1.0～6.0 with the atomic ratio of boron in described Ni (Co)-B amorphous alloy; In described Ni (Co)-M-B amorphous alloy, [Ni (Co)+M] is 3.0～10.0 with the atomic ratio of boron, and Ni (Co) is 0.1～20 with the atomic ratio of M; Described nickel (cobalt), boron and metal additive M can load on the porous carrier materials L, also can Individual existence.The specific surface area of described catalyzer is between 1.0～1500 meters
2Between/the gram.
Preparation of catalysts method provided by the invention is in 0 to 100 ℃ temperature range, preferred 0 to 40 ℃, and under agitation with Ni
2+(Co
2+) ion and metal additive M ion to be to contain BH
4 -The ion solution reduction reaction obtains described catalyzer.Specifically be with a kind of load the mixed aqueous solution of the porous carrier materials L of nickel (cobalt) salt, M salt or nickeliferous (cobalt) salt, M salt or alcoholic solution and volumetric molar concentration be 0.5～10 the BH that contains
4 -Ion solution is pressed 0.1～10.0 feed ratio contact reacts, preferred 1～4; The charge capacity of described nickel (cobalt) salt (in nickel (cobalt) ion weight) on porous carrier materials L is 0.1～20.0 heavy %; The charge capacity of M ion on porous carrier materials L is 0～20.0 heavy %; When being unsupported catalyst, in described nickeliferous (cobalt) ion, the M ionic mixing solutions, nickel (cobalt) ion, M ionic volumetric molar concentration are respectively 0.02～0.20,0.02～0.25, and Ni (Co) is 0.5～20 with the atomic ratio that feeds intake of M.Among the described preparation method,, can be with BH to unsupported catalyst
4 -Ion solution is added drop-wise in the solution of metal ion, also can be that the drips of solution with metal ion is added to BH
4 -In the ion solution; To loaded catalyst, can be with BH
4 -On ion solution the has been added to load carrier L of metal ion, also can be that solution with metal ion is added to and has flooded BH
4 -On the ionic carrier L, the two can be direct mixing, also can be slow adding, preferably adopts the mode that slowly adds, and near neutral, promptly gets catalyzer provided by the invention with the distilled water wash solid substance.
Catalyzer provided by the invention, its preferred ingredients weight proportion is: with nickel (cobalt) is 1, and then boron is 0.01～0.6, and M is 0～12, and porous carrier materials L is 0～18.
Ni of the present invention
2+Precursor be selected from nickel acetate (cobalt), nickelous chloride (cobalt), single nickel salt (cobalt) or nickelous nitrate (cobalt), preferred nickel acetate (cobalt) or nickelous chloride (cobalt); BH
4 -The ionic precursor is selected from sodium borohydride or POTASSIUM BOROHYDRIDE or its mixture.
Porous carrier materials L of the present invention refers to one or more in porous inorganic oxide, gac, the molecular sieve, described porous inorganic oxide refers to the oxide compound of periodic table of elements IV A family, I B family, II B-group, group VIB, VII family, VIII family element, one or more in wherein preferred silicon oxide, aluminum oxide, zirconium white, titanium oxide, magnesium oxide, the calcium oxide; Described molecular sieve refers to various types of Si-Al molecular sieves, hetero-atom molecular-sieve, as A type molecular sieve, X type molecular sieve, Y zeolite, ZSM series molecular sieve, beta-molecular sieve, Ω molecular sieve, phosphate aluminium molecular sieve, HTS etc., preferred porous carrier materials is silicon oxide, aluminum oxide.
Described metal additive M can be contained BH
4 -Ion solution is reduced to the metallic element of simple substance attitude one or more from corresponding salt, in the preferred elements periodictable in I B family, II B-group, group VIB, the group VIII metal element one or more, in more preferred I B family, group VIB, the group VIII metal element one or more, metal additive commonly used are one or more among Cr, Mo, W, Fe, Zn, Pt, Pd, Cu, Mn, the Ag; Described M ionic precursor can be the M positively charged ion, also can be the acid radical anion that forms with oxygen element, and when being Fe, Cu as M, described M ionic precursor can be FeCl
2, FeSO
4, CuCl
2, CuSO
4Deng; When M was Cr, Mo, W, described M ionic precursor can be Na
2CrO
4, Na
2MoO
4, Na
2WO
4Deng.
According to catalyzer provided by the invention, active component nickel (cobalt) all exists with the non-crystalline state form, and metal additive M and Ni (Co)-B forms amorphous alloy, with the form existence of Ni (Co)-M-B amorphous alloy.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 Cu K α target, be the characteristic diffraction peak of ni based amorphous 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 220 milliliters of stainless steels.Certain density D/W, catalyzer are put into autoclave, and take a breath 3 times with the hydrogen of 3.0MPa in the sealing back, to remove the oxygen in the still.Preliminary filling hydrogen 3.0MPa post-heating constant hydrogen pressure after the temperature of reaction, temperature of reaction is 50～200 ℃, more excellent 80～150 ℃, hydrogen pressure 1～10MPa, more excellent 3～10MPa, and begin to stir, stir speed (S.S.) is greater than 1000 rev/mins.Take out response sample behind the reaction certain hour and analyze its transformation efficiency.
Fig. 1 is the typical X ray diffraction spectrogram of prepared amorphous catalyst.
Specific embodiments of the invention: embodiment 1: the preparation of ultra-fine Co-B amorphous alloy catalyst
20 milliliters of the freshly prepared 1.00M POTASSIUM BOROHYDRIDE aqueous solution were at the uniform velocity splashed into Cobaltous diacetate (Co (OAc) in 10 minutes
24H
2O, 0.25M) in the solution, mol ratio is B/Co=2.5/1.In 0 ℃ and in addition violent induction stirring, gained black precipitate centrifugation is washed till neutrality with distilled water to reaction soln, promptly can be used for active testing with ice-water bath constant temperature, and catalyzer is designated as CB, and the part characterization result of this catalyzer is shown in table one.Embodiment 2: the preparation of ultra-fine Co-M-B (M=Cr, Mo, W) amorphous alloy catalyst
The freshly prepared 1.00 M POTASSIUM BOROHYDRIDE aqueous solution are splashed into nickel acetate Cobaltous diacetate (Co (OAc)
24H
2O, 0.20M) and M (Na
2CrO
4, Na
2WO
4Or Na
2MoO
40.20M) mixing solutions in, can obtain the catalyzer of required M content by the add-on of control M solution, be designated as CCB, CMB, CWB.Mol ratio is fixed as B/ (Co+3W)=5/2 during reduction.Reaction soln with ice-water bath constant temperature in 0 ℃ and in addition violent induction stirring.Gained black precipitate centrifugation is washed till neutrality with distilled water, promptly can be used for active testing, and the part characterization result of this catalyzer is shown in table one.Embodiment 3: the preparation of ultra-fine Ni-B amorphous alloy catalyst
The same CB of preparation method, but use Ni (OAc)
2(or its vitriol, hydrochloride, nitrate) is designated as NB.Embodiment 4: the preparation of loading type Ni-B/L amorphous catalyst
Carrier all boils with the 0.5 rare nitric acid that weighs % earlier and washes 2h, is washed to neutrality, and after oven dry under 110 ℃ of infrared lamps was spent the night, 350 ℃ of roasting 2h in retort furnace were crushed to 40～60 orders then again.With a certain amount of nickel chloride aqueous solution (NiCl
24H
2O, 2.00M) behind the dipping, elder generation, dries down in 110 ℃ of infrared lamps and spends the night down to drying 70 ℃ of stirred in water bath.Under vigorous stirring, drip 1.00M KBH during room temperature
4The aqueous solution, the mol ratio of boron and nickel is 3 during reduction.Catalyzer is washed till the pH value with distilled water and is about 7.0.Catalyzer is designated as NBL1, NBL2, NBL3, NBL4, NBL5, and the part characterization result of this catalyzer is shown in table two.The preparation of embodiment 5:P-2W type Ni-B and Co-B amorphous catalyst
The preparation method is with NB and CB, but uses 50% ethanolic soln, is designated as P-2WNB, P-2WCB.Glucose hydrogenation active testing example 1: ultra-fine Ni-B, Co-B, Co-M-B (M=Cr, Mo, W) amorphous catalyst
Catalyst levels is 1 gram, 50 milliliters of 50% glucose solutions, and 100 ℃ of temperature of reaction, hydrogen pressure 4.0MPa, 1000 rev/mins of stir speed (S.S.)s, hydrogenation the results are shown in table three.Glucose hydrogenation active testing example 2:P-2WNi-B, P-2WCo-B amorphous catalyst
Catalyzer is selected P-2WNB, P-2WCB for use, and all the other conditions are with glucose hydrogenation active testing example 1, and hydrogenation the results are shown in table four.Glucose hydrogenation active testing example 3: loading type Ni-B/L amorphous catalyst
Catalyst levels is 1.0g, and the Ni pickup is 50 milliliters of 10%, 50% glucose solutions, 100 ℃ of temperature of reaction, and hydrogen pressure 4.0MPa, 1000 rev/mins of stir speed (S.S.)s, hydrogenation the results are shown in table five.Glucose hydrogenation active testing example 4: the influence of pretreatment temperature
Catalyzer is selected NBL1 for use, at BH
4 -Reduction Ni
2+In differing temps roasting presoma 2h, all the other conditions are with glucose hydrogenation active testing example 3 before, and hydrogenation the results are shown in table six.Glucose hydrogenation active testing example 5: loading type Ni-M-B/L1 (M=Cr, Mo, W) amorphous catalyst
Carrier is selected SiO for use
2, all the other conditions are with glucose hydrogenation active testing example 3, and hydrogenation the results are shown in table seven.Glucose hydrogenation active testing reference examples 1:W-2 type Raney nickel catalyzator (preparation method see " Preparation of Catalyst handbook, tail is rugged, field portion is great third-class, Chemical Industry Press, Beijing, the 608th page, 1962).Except that adopting 1 gram W-2 type Raney nickel catalyzator, all the other conditions are with glucose hydrogenation active testing example 1, and hydrogenation the results are shown in table three.
Glucose hydrogenation active testing reference examples 2: loading type Ni/SiO
2Catalyzer (preparation method sees J.Chem.Soc., Faraday Trans.1,81,2733,1985).Remove and adopt 1 gram loading type Ni/ γ-Al
2O
3Outside the catalyzer, all the other conditions are with glucose hydrogenation active testing example 3, and hydrogenation the results are shown in table eight.
By the result who obtains (table three is to table eight) as can be seen, the glucose hydrogenation activity of non-crystalline state CMB catalyst series is 140% to 152% of a W-2 type Raney nickel catalyzator, and the glucose hydrogenation of loading type NMBL2 amorphous catalyst activity is 473% to 934% of a W-2 type Raney nickel catalyzator; Under the condition of same Ni consumption, Ni-W-B/SiO
2The glucose hydrogenation activity of amorphous catalyst is about the Ni/SiO that obtains with hydrogen reducing
2580%, be Ni-B/SiO
2150%; For loading type NMBL2 non-crystalline state catalyst series, higher glucose hydrogenation activity is arranged during with the 473K pre-treatment simultaneously.
The surface composition of table one, non-crystalline state CMB catalyst series, specific surface area and surface atom ratio
| Catalyzer | Body phase composite (atomic ratio) | Surface composition (atomic ratio) | Specific surface area (m 2/g) | The surface atom ratio |
| Co 0/Co 2+?????B 0/B 3+ | ||||
| ????CB ????CCB ????CMB ????CWB | ?Co 75.4B 24.6?Co 73.7Cr 1.5B 24.8?Co 74.8Mo 0.5B 24.7?Co 74.7W 1.2B 24.1 | ?Co 82.4B 17.6?Co 78.2Cr 6.8B 15.0?Co 74.0Mo 0.8B 25.2?Co 73.7W 1.5B 24.8 | ?26.2 ?42.1 ?35.0 ?43.6 | ????0.750????0.844 ????0.729????0.867 ????0.735????0.922 ????1.370????0.889 |
The part characterization result of table two, loading type NB/L amorphous catalyst
| Catalyzer | Carrier | Specific surface area (m 2/g) | Aperture () | Pore volume (cm 2/g) |
| ????NBL1 ????NBL2 ????NBL3 ????NBL4 ????NBL5 | ??SiO 2?γ-Al 2O 3Activated carbon TiO 2??ZrO 2 | ????202.55 ????132.79 ????1245.52 ????108.4 ????18.7 | ????72.58 ????135.36 ????21.68 ????149.6 ????288.9 | ????0.3542 ????0.4931 ????0.6769 ????0.3911 ????0.1318 |
The glucose hydrogenation activity of table three, non-crystalline state NCMB catalyst series and W-2 type Raney nickel catalyzator
aThe 6h inversion rate of glucose
bThe sorbyl alcohol selectivity
| Catalyzer | aTransformation efficiency (%) | bSelectivity (%) |
| W-2 type Raney nickel NB CB CCB CMB CWB | ????63.4 ????77.5 ????89.0 ????91.2 ????91.8 ????96.5 | ????100 ????100 ????100 ????100 ????100 ????100 |
Table four, non-crystalline state P-2WNB, P-2WCB catalyzer glucose hydrogenation activity
aThe 6h inversion rate of glucose
bThe sorbyl alcohol selectivity
| Catalyzer | aTransformation efficiency (%) | bSelectivity (%) |
| ????P-2WNB ????P-2WCB | ????82.1 ????96.3 | ????100 ????100 |
Table five, the active influence of loading type Ni-B/L amorphous catalyst glucose hydrogenation
aThe 6h inversion rate of glucose
bThe sorbyl alcohol selectivity
| Catalyzer | aTransformation efficiency (%) | bSelectivity (%) |
| ????NBL1 ????NBL2 ????NBL3 ????NBL4 ????NBL5 | ????30.0 ????6.5 ????7.8 ????12.2 ????10.3 | ????100 ????100 ????100 ????100 ????100 |
Table six, pretreatment temperature are to the active influence of loading type NBL1 amorphous catalyst glucose hydrogenation
aThe 6h inversion rate of glucose
bThe sorbyl alcohol selectivity
| Pretreatment temperature (K) aTransformation efficiency (%) bSelectivity (%) |
| ????373?????????????????22.0?????????????100 ????473?????????????????30.0?????????????100 ????573?????????????????19.5?????????????100 ????673?????????????????14.0?????????????100 ????773?????????????????12.4?????????????100 |
The glucose hydrogenation activity of table seven, loading type Ni-M-B/L1 (M=Cr, Mo, W) amorphous catalyst
aThe 6h inversion rate of glucose
bThe sorbyl alcohol selectivity
| Catalyzer | aTransformation efficiency (%) | bSelectivity (%) |
| ????NCBL1 ????NMBL1 ????NWBL1 | ????49.4 ????38.1 ????59.2 | ????100 ????100 ????100 |
Table eight, loading type Ni-W-B/SiO
2, Ni-Co-W-B/SiO
2, Ni/SiO
2The glucose hydrogenation activity of catalyzer
aThe 6h inversion rate of glucose
bThe sorbyl alcohol selectivity
| Catalyzer | Catalyst levels (g) | aTransformation efficiency (%) | bSelectivity (%) |
| ????(10％)Ni/SiO 2????(10％)Ni-(1％)W-B/SiO 2(10％)Ni-(10％)Co-(1％)W-B/SiO2 | ????1 ????2.0 ????1.5 | ????7.8 ????90.0 ????95.2 | ????100 ????100 ????100 |
Claims (16)
1. nickeliferous (cobalt) and amorphous alloy catalyst of boron that is used for glucose hydrogenation system sorbyl alcohol, it is characterized in that it is made up of nickel (cobalt), boron, metal additive M and porous material carrier L, the weight proportion of each component is: the consumption with nickel (cobalt) is 1, then the consumption of boron is 0.005～1.74, the consumption of M is 0～30, and the consumption of L is 0～42; Wherein nickel (cobalt) mainly exists with the form of Ni (Co)-B or Ni (Co)-M-B amorphous alloy, and metal additive M is meant and can be contained BH
4 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt.
2. catalyzer according to claim 1, it is characterized in that the weight proportion of each component is: with nickel (cobalt) is 1, and boron is 0.01～0.6, and metal additive M is 0～12, and porous carrier materials L is 0～18.
3. according to claim 1 or 2 described catalyzer, it is characterized in that described metal additive M is selected from one or more in I B family, II B-group, group VIB, the group VIII metal element in the periodic table of elements.
4. according to the described catalyzer of claim 3, it is characterized in that described metal additive M is selected from one or more among Cr, Mo, W, Fe, Pt, Pd, Cu, Zn, Mn, the Ag.
5. according to claim 1 or 2 described catalyzer, it is characterized in that described porous material L is selected from one or more in porous inorganic oxide, gac, the molecular sieve.
6. catalyzer according to claim 5 is characterized in that described porous inorganic oxide is one or more in silicon oxide, aluminum oxide, zirconium white, titanium oxide, magnesium oxide, the calcium oxide.
7. catalyzer according to claim 5 is characterized in that described molecular sieve is all kinds Si-Al molecular sieve, hetero-atom molecular-sieve.
8. according to claim 1 or 2 described catalyzer, the specific surface that it is characterized in that this catalyzer is 1.0～1500 meters
2/ gram.
9. one kind is used for glucose hydrogenation system sorbyl alcohol Preparation of catalysts method, it is characterized in that under agitation will containing Ni in 0 to 100 ℃ temperature range
2+(Co
2+) ion and metal additive M ion be from containing BH
4 -Reduction makes in the ion solution.
10. Preparation of catalysts method according to claim 9 is characterized in that with a kind of load the mixing solutions of the porous carrier materials L of nickel (cobalt) salt, M salt or nickeliferous (cobalt) salt, M salt and volumetric molar concentration are 0.5～10 BH
4 -Ion solution is pressed 0.1～10.0 ingredient proportion contact reacts, and wherein the charge capacity of nickel (cobalt) salt on L is 0.1～20.0 heavy %, and the charge capacity of M ion on L is 0～20.0 heavy %.
11., it is characterized in that, be with BH to unsupported catalyst according to claim 9 and 10 described method for preparing catalyst
4 -Ion solution is added drop-wise in the solution of metal ion, or the drips of solution of metal ion is added to BH
4 -In the ion solution; To loaded catalyst, be with BH
4 -On ion solution the has been added drop-wise to load carrier of metal ion, or the drips of solution of metal ion is added to flooded BH
4 -On the ionic carrier.
12., it is characterized in that described Ni according to claim 9 and 10 described method for preparing catalyst
2+(Co
2+) the ionic precursor is selected from nickel acetate (cobalt), nickelous chloride (cobalt), single nickel salt (cobalt) or nickelous nitrate (cobalt), BH
4 -The ionic precursor is selected from sodium borohydride or POTASSIUM BOROHYDRIDE or its mixture, and M ionic precursor is the M positively charged ion, or and the acid radical anion that forms of oxygen element.
13., it is characterized in that the described B and the atomic ratio that feeds intake of [Ni (Co)+M] are 1～4 according to claim 9 and 10 described method for preparing catalyst.
14., it is characterized in that the atomic ratio that feeds intake of Ni (Co) and M is 0.5～20 in the solution of described nickeliferous (cobalt) and metal additive M or the porous support according to claim 9 and 10 described method for preparing catalyst.
15., it is characterized in that to contain BH at 0 to 40 ℃ according to claim 9 and 10 described method for preparing catalyst
4 -Drips of solution be added in the solution or porous carrier materials of nickeliferous (cobalt) and metal additive M.
16., it is characterized in that described Ni according to claim 9 and 10 described method for preparing catalyst
2+(Co
2+) solion and BH
4 -Solion can be the aqueous solution, also can be ethanolic soln.
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302845C (en) * | 2004-03-11 | 2007-03-07 | 上海师范大学 | Co-Fe-B amorphous alloy catalyst, its preparation method and application |
| CN100465144C (en) * | 2006-12-01 | 2009-03-04 | 华南理工大学 | Method for load type amorphous ruthenium boron-containing catalyst to catalyzing hydrogenating and reducing carbonyl compound to prepare alcohol |
| CN105148922A (en) * | 2015-09-29 | 2015-12-16 | 河北大学 | NiB amorphous alloy catalyst and preparation method thereof |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
| CN109395773A (en) * | 2018-10-18 | 2019-03-01 | 安徽师范大学 | A kind of molecular sieve carried Raney nickel and preparation method thereof and the application in sorbierite is prepared in glucose hydrogenation |
| CN110041169A (en) * | 2019-05-14 | 2019-07-23 | 安徽师范大学 | The separation method of sorbierite in a kind of glucose hydrogenation liquid |
| CN110465296A (en) * | 2019-08-05 | 2019-11-19 | 中海油天津化工研究设计院有限公司 | A kind of Ni-based glucose hydrogenation catalyst and preparation method thereof |
-
2001
- 2001-01-18 CN CN01105246A patent/CN1304918A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302845C (en) * | 2004-03-11 | 2007-03-07 | 上海师范大学 | Co-Fe-B amorphous alloy catalyst, its preparation method and application |
| CN100465144C (en) * | 2006-12-01 | 2009-03-04 | 华南理工大学 | Method for load type amorphous ruthenium boron-containing catalyst to catalyzing hydrogenating and reducing carbonyl compound to prepare alcohol |
| CN105148922A (en) * | 2015-09-29 | 2015-12-16 | 河北大学 | NiB amorphous alloy catalyst and preparation method thereof |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
| CN109395773A (en) * | 2018-10-18 | 2019-03-01 | 安徽师范大学 | A kind of molecular sieve carried Raney nickel and preparation method thereof and the application in sorbierite is prepared in glucose hydrogenation |
| CN110041169A (en) * | 2019-05-14 | 2019-07-23 | 安徽师范大学 | The separation method of sorbierite in a kind of glucose hydrogenation liquid |
| CN110041169B (en) * | 2019-05-14 | 2022-05-10 | 安徽师范大学 | Method for separating sorbitol from glucose hydrogenation reaction liquid |
| CN110465296A (en) * | 2019-08-05 | 2019-11-19 | 中海油天津化工研究设计院有限公司 | A kind of Ni-based glucose hydrogenation catalyst and preparation method thereof |
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