CN109395773A - A kind of molecular sieve carried Raney nickel and preparation method thereof and the application in sorbierite is prepared in glucose hydrogenation - Google Patents
A kind of molecular sieve carried Raney nickel and preparation method thereof and the application in sorbierite is prepared in glucose hydrogenation Download PDFInfo
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- CN109395773A CN109395773A CN201811216116.3A CN201811216116A CN109395773A CN 109395773 A CN109395773 A CN 109395773A CN 201811216116 A CN201811216116 A CN 201811216116A CN 109395773 A CN109395773 A CN 109395773A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
本发明公开了一种分子筛负载镍催化剂及其制备方法和应用，所述制备方法包括以下步骤：(1)将分子筛焙烧，得到活化后的分子筛载体；(2)将活化后的分子筛载体于镍盐溶液中浸渍，干燥，煅烧；其中，分子筛为HZSM‑5、SAPO‑11、SAPO‑34和MCM‑21中的一种或多种。该分子筛负载镍催化剂无需对催化剂进行氢气还原，仅需温和条件即可对催化剂进行有效还原，还原的过程和对葡萄糖进行氢化制备山梨醇的催化过程同时进行。与现有技术相比，葡萄糖转化率高、山梨醇选择性好。
The invention discloses a molecular sieve supported nickel catalyst and a preparation method and application thereof. The preparation method comprises the following steps: (1) calcining the molecular sieve to obtain an activated molecular sieve carrier; (2) placing the activated molecular sieve carrier on nickel Impregnation in a salt solution, drying, and calcination; wherein, the molecular sieve is one or more of HZSM-5, SAPO-11, SAPO-34 and MCM-21. The molecular sieve-supported nickel catalyst does not need to perform hydrogen reduction on the catalyst, and only needs mild conditions to effectively reduce the catalyst, and the reduction process and the catalytic process of hydrogenating glucose to prepare sorbitol are performed simultaneously. Compared with the prior art, the glucose conversion rate is high and the sorbitol selectivity is good.
Description
Technical field
The present invention relates to molecular sieve carried Raney nickels, and in particular, to a kind of molecular sieve carried Raney nickel and its system
Preparation Method and the application in sorbierite is prepared in glucose hydrogenation.
Background technique
Sorbierite is a kind of important fine chemicals, can be widely applied to medicine, food and chemical field, especially ties up
Synthesis, sweetener, wetting agent, stabilizer and the resins synthesis etc. of raw element C, in addition, sorbierite can also pass through hydrocracking
Petrochemical materials such as ethylene glycol, 1,2-PD etc. is produced, meanwhile, sorbierite can also prepare lightweight alkane by hydrogenation deoxidation
Hydrocarbon, alkene and be used for the fields such as novel biological fuel.
Currently, sorbierite is mainly restored by Catalytic Hydrogenation of Glucose come and glucose is using cheap fibre
Element, starch or biomass are tieed up to obtain, the synthesis of sorbierite has been a concern.Industrially prepare sorbierite method be generally
Glucose hydrogenation catalysis is carried out using Raney's nickel alloy series catalysts, while needing to carry out under conditions of high pressure hydrogen.In early days
The Chinese invention patent CN1062851C used discloses a kind of nickel alloy catalyst, reaction temperature be 100-150 DEG C, H2 press
Power is that can effectively convert glucose under 3-12MPa.But such system is more harsh to catalyst use, is being catalyzed
Agent has problem of environmental pollution during making and using, and the continuous-stable of catalyst performance also needs emphasis to consider.In view of expensive
The price is very expensive for metal, and the reaction condition of catalyst need to carry out under high pressure hydrogen, more demanding to consersion unit, simultaneously
The performance of catalyst is still to be improved, causes the actual production effect of sorbierite not ideal enough.
To glucose hydrogenation reaction, usually only metal simple-substance catalyst just has hydrogenating reduction ability, therefore catalyst exists
In preparation process, it usually needs carry out hydrogen high temperature reduction, metal oxide is reduced into metal simple-substance.And catalyst is passing through
During hydrogen high temperature reduction, catalyst particle size would generally obviously grow up and reunite sintering, cause performance to decline, not only such as
This, existing noble metal catalyst such as Pd/C, Ru/C is expensive, high production cost.
Therefore it provides a kind of catalyst and preparation method thereof, the catalyst do not need to carry out hydrogen high temperature reduction and can
With mild method reduction to play catalytic action, and the catalyst is during preparing sorbierite with glucose hydrogenation,
The preparation method for not needing the reaction condition of the high requirements on the equipment such as high-pressure hydrogenation is current problem to be solved.
Summary of the invention
System is hydrogenated the object of the present invention is to provide a kind of molecular sieve carried Raney nickel and preparation method thereof and in glucose
Application in standby sorbierite, the molecular sieve carried Raney nickel are not necessarily to carry out hydrogen reducing to catalyst, on the one hand, simplify catalysis
Agent preparation process shortens the catalyst preparation period, can also substantially reduce energy consumption and improve the feature of environmental protection, on the other hand, the present invention
In catalyst be passed through hydrogen without high pressure-temperature in reduction, reduction process carries out in the use process of catalyst, it is only necessary to
Temperate condition can effectively restore catalyst, the process of reduction and carry out the catalysis that hydrogenation prepares sorbierite to glucose
Process carries out simultaneously.The partial size of catalyst is smaller, also avoids growing up for catalyst particle size, substantially increases catalyst performance.
It is mild to glucose hydrogenation reaction condition using the molecular sieve carried Raney nickel, it is not necessarily to high temperature, high pressure, and do not have to additionally be passed through
The synthesis of sorbierite can be realized in hydrogen.Compared with prior art, inversion rate of glucose is high, sorbierite is selectively good.Addition
Molecular sieve carried Raney nickel can mutually be separated by conventional solid-liquid separate mode with reaction system after the completion of reaction, be conducive to product
The purifying of sorbierite can simplify glucose hydrogenation and produce sorbitol production technique.
To achieve the goals above, the present invention provides a kind of preparation method of molecular sieve carried Raney nickel, the systems
Preparation Method is the following steps are included: (1) roasts molecular sieve, the molecular sieve carrier after being activated；(2) by the molecular sieve after activation
Carrier impregnates in nickel salt solution, dry, calcining；Wherein, in molecular sieve HZSM-5, SAPO-11, SAPO-34 and MCM-21
It is one or more.
The present invention also provides a kind of molecular sieve carried Raney nickels being prepared according to previously described preparation method.
Moreover, it hydrogenates and prepares in glucose the present invention also provides a kind of previously described molecular sieve carried Raney nickel
Application in sorbierite, it is 5~10% glucose solutions, molecular sieve carried Raney nickel that the application, which includes: by mass fraction,
It is mixed with borohydride salts, adjusts the pH to 2-10 of mixed liquor, react 1-4h in 60-100 DEG C of heating；Wherein, in glucose solution
Glucose, molecular sieve carried Raney nickel and borohydride salts mass ratio be 100:8-12:1-5.
Through the above technical solutions, the present invention provides a kind of molecular sieve carried Raney nickel and preparation method thereof and in grape
Sugared hydrogenation prepares the application in sorbierite, which is not necessarily to carry out hydrogen reducing to catalyst, on the one hand,
Simplify catalyst preparation process, shorten the catalyst preparation period, energy consumption can also be substantially reduced and improves the feature of environmental protection, another party
Face, the catalyst in the present invention are passed through hydrogen without high pressure-temperature in reduction, and reduction process is in the use process of catalyst
Carry out, it is only necessary to temperate condition can effectively restore catalyst, the process of reduction and to glucose carry out hydrogenation prepare mountain
The catalytic process of pears alcohol carries out simultaneously.The partial size of catalyst is smaller, also avoids growing up for catalyst particle size, substantially increases and urge
Agent performance.It is mild to glucose hydrogenation reaction condition using the molecular sieve carried Raney nickel, it is not necessarily to high temperature, high pressure, and not
With additionally hydrogen is passed through, the synthesis of sorbierite can be realized.Compared with prior art, inversion rate of glucose height, sorbierite selection
Property is good.The molecular sieve carried Raney nickel of addition can pass through conventional solid-liquid separate mode and reaction system phase point after the completion of reaction
From can simplify glucose hydrogenation and produce sorbitol production technique conducive to the purifying of product sorbierite.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the high performance liquid chromatography that catalyst hydrogenated glucose prepares sorbierite in embodiment 2.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of molecular sieve carried Raney nickel, the preparation method includes following step
It is rapid: (1) to roast molecular sieve, the molecular sieve carrier after being activated；(2) by the molecular sieve carrier after activation in nickel salt solution
Dipping, dry, calcining；Wherein, one of molecular sieve HZSM-5, SAPO-11, SAPO-34 and MCM-21 or a variety of.
Through the above technical solutions, the present invention provides a kind of molecular sieve carried Raney nickel and preparation method thereof and in grape
Sugared hydrogenation prepares the application in sorbierite, which is not necessarily to carry out hydrogen reducing to catalyst, on the one hand,
Simplify catalyst preparation process, shorten the catalyst preparation period, energy consumption can also be substantially reduced and improves the feature of environmental protection, another party
Face, the catalyst in the present invention are passed through hydrogen without high pressure-temperature in reduction, and reduction process is in the use process of catalyst
Carry out, it is only necessary to temperate condition can effectively restore catalyst, the process of reduction and to glucose carry out hydrogenation prepare mountain
The catalytic process of pears alcohol carries out simultaneously.The partial size of catalyst is smaller, also avoids growing up for catalyst particle size, substantially increases and urge
Agent performance.It is mild to glucose hydrogenation reaction condition using the molecular sieve carried Raney nickel, it is not necessarily to high temperature, high pressure, and not
With additionally hydrogen is passed through, the synthesis of sorbierite can be realized.Compared with prior art, inversion rate of glucose height, sorbierite selection
Property is good.The molecular sieve carried Raney nickel of addition can pass through conventional solid-liquid separate mode and reaction system phase point after the completion of reaction
From can simplify glucose hydrogenation and produce sorbitol production technique conducive to the purifying of product sorbierite.
In the above-mentioned technical solutions, the mass ratio of nickel salt can be in wider model in the molecular sieve carrier and nickel salt solution after activation
Enclose it is interior selected, in a kind of preferred embodiment of the present invention, in order to improve inversion rate of glucose and to the choosing of sorbierite
Selecting property, the mass ratio of nickel salt is 100:5-10 in the molecular sieve carrier and nickel salt solution after activation.
In the above-mentioned technical solutions, the mass concentration of nickel salt can be selected in a wider range, of the invention a kind of excellent
In the embodiment of choosing, in order to improve inversion rate of glucose and to the selectivity of sorbierite, the mass concentration of nickel salt is 10-
300g/L。
In the above-mentioned technical solutions, the roasting condition in step (1) can be selected in a wider range, in the present invention one
Maturing temperature in kind of preferred embodiment, in order to improve inversion rate of glucose and to the selectivity of sorbierite, in step (1)
It is 300~600 DEG C.
Under the above conditions, it for calcining time in step (1), can be adjusted in a wider range, in order to improve Portugal
Grape sugar conversion ratio and selectivity to sorbierite, calcining time are 2~5 hours.
In the above-mentioned technical solutions, the calcination condition in step (2) can be selected in a wider range, in this hair
Calcining in a kind of bright preferred embodiment, in order to improve inversion rate of glucose and to the selectivity of sorbierite, in step (2)
Temperature is 500~600 DEG C.
Under the above conditions, it for calcination time in step (2), can be adjusted in a wider range, in order to improve Portugal
Grape sugar conversion ratio and selectivity to sorbierite, the calcination time in step (2) is 4~8h.
In the above-mentioned technical solutions, it for dip time, can be adjusted, turn to improve glucose in a wider range
Rate and selectivity to sorbierite, dip time 10-12h.
In the above-mentioned technical solutions, for nickel salt, can there are many selections, as long as can be dissolved in aqueous solution, Ji Keshi
The existing present invention, in a kind of preferred embodiment of the present invention, in order to improve inversion rate of glucose and to the selectivity of sorbierite,
Nickel salt is nickel nitrate and/or nickel acetate.
The present invention also provides a kind of molecular sieve carried Raney nickels being prepared according to previously described preparation method.
Through the above technical solutions, the present invention provides a kind of molecular sieve carried Raney nickel and preparation method thereof and in grape
Sugared hydrogenation prepares the application in sorbierite, which is not necessarily to carry out hydrogen reducing to catalyst, on the one hand,
Simplify catalyst preparation process, shorten the catalyst preparation period, energy consumption can also be substantially reduced and improves the feature of environmental protection, another party
Face, the catalyst in the present invention are passed through hydrogen without high pressure-temperature in reduction, and reduction process is in the use process of catalyst
Carry out, it is only necessary to temperate condition can effectively restore catalyst, the process of reduction and to glucose carry out hydrogenation prepare mountain
The catalytic process of pears alcohol carries out simultaneously.The partial size of catalyst is smaller, also avoids growing up for catalyst particle size, substantially increases and urge
Agent performance.It is mild to glucose hydrogenation reaction condition using the molecular sieve carried Raney nickel, it is not necessarily to high temperature, high pressure, and not
With additionally hydrogen is passed through, the synthesis of sorbierite can be realized.Compared with prior art, inversion rate of glucose height, sorbierite selection
Property is good.The molecular sieve carried Raney nickel of addition can pass through conventional solid-liquid separate mode and reaction system phase point after the completion of reaction
From can simplify glucose hydrogenation and produce sorbitol production technique conducive to the purifying of product sorbierite.
Moreover, it hydrogenates and prepares in glucose the present invention also provides a kind of previously described molecular sieve carried Raney nickel
Application in sorbierite, it is 5~10% glucose solutions, molecular sieve carried Raney nickel that the application, which includes: by mass fraction,
It is mixed with borohydride salts, adjusts the pH to 2-10 of mixed liquor, react 1-4h in 60-100 DEG C of heating；Wherein, in glucose solution
Glucose, molecular sieve carried Raney nickel and borohydride salts mass ratio be 100:8-12:1-5.
Through the above technical solutions, the present invention provides a kind of molecular sieve carried Raney nickel and preparation method thereof and in grape
Sugared hydrogenation prepares the application in sorbierite, which is not necessarily to carry out hydrogen reducing to catalyst, on the one hand,
Simplify catalyst preparation process, shorten the catalyst preparation period, energy consumption can also be substantially reduced and improves the feature of environmental protection, another party
Face, the catalyst in the present invention are passed through hydrogen without high pressure-temperature in reduction, and reduction process is in the use process of catalyst
Carry out, it is only necessary to temperate condition can effectively restore catalyst, the process of reduction and to glucose carry out hydrogenation prepare mountain
The catalytic process of pears alcohol carries out simultaneously.The partial size of catalyst is smaller, also avoids growing up for catalyst particle size, substantially increases and urge
Agent performance.It is mild to glucose hydrogenation reaction condition using the molecular sieve carried Raney nickel, it is not necessarily to high temperature, high pressure, and not
With additionally hydrogen is passed through, the synthesis of sorbierite can be realized.Compared with prior art, inversion rate of glucose height, sorbierite selection
Property is good.The molecular sieve carried Raney nickel of addition can pass through conventional solid-liquid separate mode and reaction system phase point after the completion of reaction
From can simplify glucose hydrogenation and produce sorbitol production technique conducive to the purifying of product sorbierite.
The condition of above-mentioned heating reaction can be adjusted in a wider range, in order to improve inversion rate of glucose and right
The selectivity of sorbierite heats the condition of reaction are as follows: reacts 1-2h in 80-100 DEG C of heating.
And for borohydride salts, can be selected in a wider range, it is preferable that borohydride salts be sodium borohydride and/
Or potassium borohydride.
In order to improve inversion rate of glucose and to the selectivity of sorbierite, it is highly preferred that the pH to 7-10 of mixed liquor.
The present invention will be described in detail by way of examples below.
Embodiment 1
The preparation method of molecular sieve carried Raney nickel, the preparation method comprises the following steps:
(1) SAPO-11 molecular sieve is roasted 3.5 hours in 450 DEG C, the molecular sieve carrier after being activated；
(2) molecular sieve carrier after activating 0.15g impregnates 11h in the nickel acetate solution that mass concentration is 75g/L, does
It is dry, in 550 DEG C of 4~8h of calcining；The mass ratio of nickel nitrate is 100:5 in molecular sieve carrier and nickel salt solution after activation, obtains 5%
NiO/SAPO-11 catalyst.
Embodiment 2
Catalyst is prepared according to the method for embodiment 1, the difference is that SAPO-11 molecular sieve is replaced with HZSM-5 molecule
Sieve, obtains 5%NiO/HZSM-5 catalyst.
Embodiment 3
Catalyst is prepared according to the method for embodiment 1, the difference is that SAPO-11 molecular sieve is replaced with MCM-21 molecule
Sieve, obtains 5%NiO/MCM-21 catalyst.
Embodiment 4
Catalyst is prepared according to the method for embodiment 1, unlike, SAPO-11 molecular sieve is replaced with into SAPO-34 molecule
Sieve, and nickel acetate is replaced with into nickel nitrate, obtain 5%NiO/SAPO-34 catalyst.
Embodiment 5
Catalyst is prepared according to the method for embodiment 1, unlike, it will be in the molecular sieve carrier and nickel salt solution after activation
The mass ratio of nickel nitrate is adjusted to obtain 10%NiO/SAPO-11 catalyst for 100:10.
Application examples 1
Respectively measure 30ml mass fraction be 5% glucose solution be added in reaction kettle, then add sodium borohydride and
Catalyst in 0.15g embodiment 1-5, the mass ratio of glucose and sodium borohydride in glucose solution are 100:2, and adjustment is mixed
Close the pH to 7 of liquid, after sealing reaction kettle, reaction temperature is set in 80 DEG C, react 1 hour, product using high performance liquid chromatography into
Row analysis, wherein catalyst in embodiment 1-5 the results are shown in Table 1 to what glucose hydrogenation prepared sorbierite, be corresponding in turn to
S1-S5。
Wherein, mixed liquor uses efficient liquid phase chromatographic analysis, using Bole's HPX-87H liquid-phase chromatographic column, with 5mmol sulfuric acid
For mobile phase, flow rate of mobile phase is 0.55ml per minute.Catalyst hydrogenated glucose prepares the efficient liquid of sorbierite in embodiment 2
Phase chromatographic results such as Fig. 1 shows, it can be seen that, preparation method of the invention has synthesized sorbierite.
The conversion ratio of glucose and the selectivity of sorbierite are calculated, the results are shown in Table 1.Calculation formula is as follows:
Application examples 2
Catalyst in Example 2 carries out glucose hydrogenation according to the method in application examples 1 and prepares sorbierite, different
It is to adjust the pH of mixed liquor to 2, acquired results are shown in Table S6 in 1.
Application examples 3
Catalyst in Example 2 carries out glucose hydrogenation according to the method in application examples 1 and prepares sorbierite, different
It is to adjust the pH of mixed liquor to 10, acquired results are shown in Table S7 in 1.
Application examples 4
Catalyst in Example 1 carries out glucose hydrogenation according to the method in application examples 1 and prepares sorbierite, different
It is that the mass ratio of the glucose and sodium borohydride in glucose solution is adjusted to 100:1.5, acquired results are shown in Table S8 in 1.
Table 1
| Number | Inversion rate of glucose (%) | Sorbierite selectivity (%) |
| S1 | 99 | 90.2 |
| S2 | 55.5 | 71.8 |
| S3 | 50.6 | 77.8 |
| S4 | 52.1 | 86.6 |
| S5 | 90.2 | 89.1 |
| S6 | 95.7 | 68.8 |
| S7 | 100 | 93.3 |
| S8 | 30.9 | 100 |
By above-described embodiment and corresponding application examples as it can be seen that catalyst of the invention is in the presence of sodium borohydride,
Glucose can be hydrogenated as sorbierite under mild conditions.The solid catalyst that the present invention uses after the completion of reaction can
Solid catalyst can be separated by simple filter type, simplify the purifying process of product.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of molecular sieve carried Raney nickel, which is characterized in that the preparation method comprises the following steps:
(1) molecular sieve is roasted, the molecular sieve carrier after being activated；
(2) molecular sieve carrier after activation is impregnated in nickel salt solution, dry, calcining；
Wherein, one of molecular sieve HZSM-5, SAPO-11, SAPO-34 and MCM-21 or a variety of.
2. preparation method according to claim 1, wherein the matter of nickel salt in the molecular sieve carrier and nickel salt solution after activation
Amount is than being 100:5-10.
3. preparation method according to claim 2, wherein the mass concentration of nickel salt is 10-300g/L.
4. preparation method according to claim 1-3, wherein the roasting condition in step (1) includes: that temperature is
300~600 DEG C；And/or the time is 2~5 hours.
5. preparation method according to claim 1-3, wherein the calcination condition in step (2) includes: that temperature is
500~600 DEG C；And/or the time is 4~8h；
And/or dip time 10-12h.
6. preparation method according to claim 1-3, wherein nickel salt is nickel nitrate and/or nickel acetate.
7. the molecular sieve carried Raney nickel that preparation method according to claim 1-6 is prepared.
8. molecular sieve carried Raney nickel as claimed in claim 7 prepares the application in sorbierite, feature in glucose hydrogenation
It is, it is 5~10% glucose solutions, molecular sieve carried Raney nickel and borohydride salts that the application, which includes: by mass fraction,
Mixing, adjusts the pH to 2-10 of mixed liquor, reacts 1-4h in 60-100 DEG C of heating；
Wherein, the mass ratio of the glucose in glucose solution, molecular sieve carried Raney nickel and borohydride salts is 100:8-12:
1-5。
9. application according to claim 8, wherein heat the condition of reaction are as follows: react 1-2h in 80-100 DEG C of heating.
10. application according to claim 8 or claim 9, wherein borohydride salts are sodium borohydride and/or potassium borohydride.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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