CN101381280B - Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol - Google Patents
Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol Download PDFInfo
- Publication number
- CN101381280B CN101381280B CN2007100127093A CN200710012709A CN101381280B CN 101381280 B CN101381280 B CN 101381280B CN 2007100127093 A CN2007100127093 A CN 2007100127093A CN 200710012709 A CN200710012709 A CN 200710012709A CN 101381280 B CN101381280 B CN 101381280B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyzer
- solution
- hydrogenolysis
- nickel salt
- 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.)
- Expired - Fee Related
Links
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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to application of an Ni-based supported catalyst to a hydrogenolysis reaction of glycerol for preparing 1,2-propanediol and glycol, in particular to the application of the Ni-based supported catalyst to the hydrogenolysis process of the glycerol, wherein the catalyst uses Ni as a main active component, a carrier is a silica-alumina molecular sieve, a mesoporous molecular sieve or a phospho-aluminate molecular sieve, and the content of the active component Ni in the catalyst is between 1 and 25 weight percent; and the catalyst used in the hydrogenolysis reaction of the glycerol for preparing the 1,2-propanediol and the glycol can realize the high-activity high-selectivity hydrocracking of the glycerol. The Ni-based supported catalyst is a non-precious metal catalyst with simple preparation method and higher catalytic activity and selectivity.
Description
Technical field
The present invention is a hydrogenolysis of glycyl alcohol system 1, the reaction of 2-propylene glycol and ethylene glycol, the application of specifically a kind of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol.
Background technology
1, the 2-propylene glycol (is called for short 1,2-PDO) be a kind of very important industrial chemicals, be mainly used in the intermediate of producing unsaturated polyester, Resins, epoxy, urethane resin etc., because its viscosity and good hygroscopicity and nontoxic again, have good bactericidal properties, wettability, solvability, be widely used as moisture adsorbent, antifreezing agent, lubricant and solvent in food, medicine, makeup and other field of hygiene products.In recent years, to 1, the demand of 2-propylene glycol increased day by day.And along with the fast development that unsaturated polyester resin is produced, its demand also can further increase.
Present 1, the 2-propylene glycol mainly adopts the preparation of propylene oxide direct hydration method, because the preparation of propylene oxide is to be raw material with the propylene, mass production mainly relies on consumption of petroleum resources, in addition, in the propylene oxide direct hydration method, adopt sulfuric acid to make catalyzer usually, environment is caused serious pollution.Therefore, develop non-petroleum path, novel environmental close friend's 1,2-propylene glycol preparation technology is the petrochemical complex route of raw material with the displaced loop Ethylene Oxide, has great importance and favorable industrial application prospect.
Ethylene glycol is the fine chemical material of a kind of important energy liquid fuel or high added value, has very to use widely in Chemical Manufacture and daily life.It is main raw materials such as trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive, also can be used for solvent, wetting agent, frostproofer and the thermal conductor etc. of spices.Whole world ethylene glycol annual requirement is with 6%～7% speed increment, and the method for producing ethylene glycol both at home and abroad mainly is the oxyethane direct hydration method, raw material ethene cost height, and energy consumption is big, and equipment is perishable and environmental pollution is serious.
Glycerol is the by product of production of biodiesel process, and output is about 10% of biofuel.Along with the increase of yield of biodiesel, also will increase considerably as the output of the glycerol of by product.Utilize the glycerol catalytic hydrogenolysis to generate 1,2-propylene glycol and ethylene glycol, this method not only can improve the economy of production of biodiesel process, and raw material is a renewable resources.Therefore, the hydrogenolysis of glycerol is the preparation 1 of an environmental protection, the technological line of 2-propylene glycol and ethylene glycol.
In recent years, relevant hydrogenolysis of glycyl alcohol preparation 1, the research of 2-propylene glycol and ethylene glycol has more report.But reaction conditions is relatively harsher, generally need (carry out under 20～30MPa) conditions, as patent DE 4 302 464, US 5 214 219, US5 616 817 at high pressure.The yield of the product that has is lower, as patent US 4 642 394, adopts the homogeneous catalyst of tungstenic and group VIII metal, at 1.4～68.9MPa, under 100～200 ℃ of conditions, organic bases is a solvent, carry out glycerol hydrocracking reaction, 1, the yield of 2-propylene glycol is no more than 20%.The employing precious metal that also has is made catalyzer, costs an arm and a leg, as patent US 5 266 181, US 6 080 898.So develop a kind of non-precious metal catalyst efficiently, make the preparation 1 of glycerol highly selective under the hydroconversion condition of gentleness, 2-propylene glycol and ethylene glycol are significant and challenging problems.
Summary of the invention
The object of the present invention is to provide the application of a kind of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol, adopt non-precious metal catalyst, its preparation method is simple, has advantages of high catalytic activity.With the glycerin solution is raw material, and under gentle relatively reaction conditions, to 1,2-propylene glycol and ethylene glycol have higher selectivity.
For achieving the above object, the technical solution used in the present invention is:
The application of a kind of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol, catalyzer is to be main active component with Ni, the porous support that adopts is Si-Al molecular sieve, mesopore molecular sieve or phosphate aluminium molecular sieve, and the content of active component nickel in catalyzer is 1～25wt%; This catalyzer is used for hydrogenolysis of glycyl alcohol prepared in reaction 1, and 2-propylene glycol and ethylene glycol can be realized the high-activity high-selectivity hydrocracking of glycerol.
Described Si-Al molecular sieve is beta-molecular sieve, X type molecular sieve, Y zeolite or the mordenite with twelve-ring pore passage structure, perhaps has ZSM-5, ZSM-22 or the ZSM-23 of ten-ring pore passage structure, perhaps A type molecular sieve; Described mesopore molecular sieve is MCM-41 or SBA-15; Described phosphate aluminium molecular sieve is SAPO-11; The X or the Y zeolite that preferably have octahedral zeolite cage, twelve-ring structure;
Carrier can be the mixture of H type, Na type or H type and Na type;
Also be added with boron in the described catalyzer as auxiliary agent, wherein the mol ratio of boron and nickel is 1.0～10.0;
Described catalyzer adopts the method preparation of dipping, preferred incipient impregnation;
1) takes by weighing the soluble nickel salt impregnating porous carrier solution in proportion, in 100～130 ℃ of oven dry;
2) activation of catalyzer:
A. adopt the hydrogen reducing activation: in 450～750 ℃, in hydrogen atmosphere, reduced 4～7 hours, make loaded catalyst;
Perhaps B. adopts POTASSIUM BOROHYDRIDE and/or sodium borohydride reduction: in-5～100 ℃ scope, under alkaline condition, is the BH that contains of 0.1～10.0M with volumetric molar concentration with nickeliferous porous support
4 -Solution drip, fully stir and carry out reduction reaction, generate black solid, what dripped contains BH
4 -Solution and the mol ratio of nickel salt be 1.0～10.0; The black solid that obtains is washed with distilled water to neutrality, makes loaded catalyst.
Described nickel salt solution refers to the aqueous solution of nickel salt, and described nickel salt is selected from one or more in nickelous chloride, single nickel salt, nickel acetate, the nickelous nitrate, preferred nickelous chloride or nickelous nitrate; Contain BH
4 -Solution be BH
4 -The aqueous solution, described BH
4 -Precursor be selected from a kind of in sodium borohydride, the POTASSIUM BOROHYDRIDE, perhaps select both mixtures; Reductive condition under alkaline condition, is the contain BH of 0.2～2.0M with volumetric molar concentration preferably at 0～40 ℃
4 -Solution reduction; What dripped contains BH
4 -Solution and the mol ratio of nickel salt be preferably 1.0～6.0.
In the presence of the loaded catalyst after the activation, at 100～300 ℃, under 1.0～10.0MPa hydrogen pressure, be solvent with water, carry out the hydrogenolysis of glycyl alcohol reaction, prepared catalyzer is to 1, and 2-propylene glycol and ethylene glycol have very high selectivity and yield.
Catalyst activity provided by the invention can be tested with the following method:
In the 600ml autoclave, investigate catalyst activity.Certain density glycerin solution, catalyzer are put into still, seal the back with the air in the 1.0MPa hydrogen exchange still, 4～5 times repeatedly.Valve-off then, heated constant temperature pour hydrogen again to required pressure to needed temperature of reaction, temperature of reaction is 100～300 ℃, and preferred 150～250 ℃, hydrogen pressure is 1.0～10.0MPa, preferred 4.0～8.0MPa.Open mechanical stirrer after reaching balance, reaction picks up counting.Behind the reaction certain hour, take out response sample,, calculate the transformation efficiency and the product selectivity of reaction then with the gas-chromatography qualitative and quantitative analysis.
The present invention has following advantage:
Catalyzer of the present invention is to be the loaded catalyst of main active component with Ni, and this catalyzer is used for the hydrogenolysis of glycyl alcohol reaction, can realize the high-activity high-selectivity hydrocracking of glycerol under the condition of gentleness.The present invention is a non-precious metal catalyst, than noble metal catalyst, and this catalyzer with low cost, and its preparation technology is simple.In hydrogenolysis of glycyl alcohol preparation 1, in 2-propylene glycol and the glycol reaction, have advantages of high catalytic activity and selectivity.Wherein, 86.6% transformation efficiency and 94.6% selectivity under 200 ℃, the condition of 6.0MPa, have been realized.
Embodiment
Below come the present invention is given further instruction (agents useful for same is an analytical pure in the example) by example, it should be noted that the following examples only as illustrating, content of the present invention is not limited thereto.
In the following example, glycerol transformation efficiency and selectivity of product are defined by following formula.
It is HP 4890D gas chromatograph that assay products is formed used analytical instrument.
The present invention will be described in detail with embodiment below
Embodiment 1
Take by weighing the six water nickelous chlorides of 8.1g, add quantitative distilled water and be configured to nickel chloride solution, and the carrier of dipping 20.0g NaM, in 120 ℃ of oven dry, get nickeliferous carrier; Get 100ml 1.0MKBH
4The aqueous solution that contains 0.2MNaOH, in ice-water bath with KBH
4The aqueous solution is added drop-wise in the nickeliferous carrier, and reaction is carried out immediately and emitted gas, drip finish after, gas not had is emitted, and shows that reaction finishes, the solid product that obtains with distilled water wash promptly gets catalyzer provided by the invention to there not being acid group.
Hydrogenolysis of glycyl alcohol is reflected in the Monel autoclave that volume is 600ml and carries out.Reactor is used hydrogen exchange in advance, adds the 40g glycerol then, 120g water, catalyzer 2.0g (by metal).At 200 ℃, 6.0MPa hydrogen reacts under the rotating speed 500rpm condition, and the reaction times is 10 hours.Test result is listed in table 1.
Comparative Examples 1
The preparation of unsupported catalyst: take by weighing the six water nickelous chlorides of 8.1g, add quantitative distilled water and be configured to nickel chloride solution, get 100ml 1.0MKBH
4The aqueous solution that contains 0.2MNaOH, in ice-water bath with KBH
4The aqueous solution is added drop-wise in the nickeliferous solution, and reaction is carried out immediately and emitted gas, drip finish after, gas not had is emitted, and shows that reaction finishes, the solid product that obtains with distilled water wash promptly gets catalyzer provided by the invention to there not being acid group.Reaction conditions is with embodiment 1, and test result is listed in table 1.
Embodiment 2
Except carrier being changed into the H beta molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 3
Except carrier being changed into NaX type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 4
Except carrier being changed into HX type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 5
Except carrier being changed into NaY type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 6
Except carrier being changed into HY type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 7
Except carrier being changed into HUSY type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 8
Except carrier being changed into HSSY type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 9
Take by weighing a certain amount of six water nickelous nitrates, add quantitative distilled water and be configured to nickel nitrate solution, and dipping type ZSM 5 molecular sieve carrier, in 100 ℃ of oven dry, get 1wt%Ni/ZSM-5; Under 100 ℃ of conditions, with 0.1MNaBH
4The aqueous solution that contains 0.2MNaOH is added drop-wise among the 1wt%Ni/ZSM-5, and reaction is carried out and releasing hydrogen gas immediately, fully stirs and carries out reduction reaction, generates black solid, the NaBH that is dripped
4Solution and the mol ratio of nickel salt be 1.0, catalyzer provided by the invention.
Hydrogenolysis of glycyl alcohol is reflected in the Monel autoclave that volume is 600ml and carries out.Reactor is used hydrogen exchange in advance, adds the 40g glycerol then, 120g water, catalyzer 2.0g (by metal).At 100 ℃, 1.0MPa hydrogen reacts under the rotating speed 500rpm condition, and the reaction times is 10 hours.Test result is listed in table 1.
Embodiment 10
Take by weighing a certain amount of six water nickelous nitrates, add quantitative distilled water and be configured to nickel nitrate solution, and dipping ZSM-22 type molecular sieve carrier, in 130 ℃ of oven dry, get 25wt%Ni/ZSM-22; Under-5 ℃ of conditions, with 10.0MNaBH
4The aqueous solution that contains 0.2MNaOH is added drop-wise among the 25wt%Ni/ZSM-22, and reaction is carried out and releasing hydrogen gas immediately, fully stirs and carries out reduction reaction, generates black solid, the NaBH that is dripped
4Solution and the mol ratio of nickel salt be 10, catalyzer provided by the invention.
Hydrogenolysis of glycyl alcohol is reflected in the Monel autoclave that volume is 600ml and carries out.Reactor is used hydrogen exchange in advance, adds the 40g glycerol then, 120g water, catalyzer 2.0g (by metal).At 300 ℃, 10.0MPa hydrogen reacts under the rotating speed 500rpm condition, and the reaction times is 10 hours.Test result is listed in table 1.
Embodiment 11
Except carrier being changed into ZSM-23 type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 12
Except carrier being changed into SAPO-11 type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
Embodiment 13
Except carrier being changed into CaA type molecular sieve, other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 1.
The hydrogenolysis of glycyl alcohol performance of each catalyzer of table 1 embodiment 1～13 and Comparative Examples
| Catalyzer | Bearer type | Transformation efficiency % | The overall selectivity % of primary product | The distribution % of primary product | |
| 1, the 2-propylene glycol | Ethylene glycol | ||||
| Embodiment 1 | NaM | 14.0 | 70.0 | 56.7 | 13.3 |
| Comparative Examples 1 | - | 22.9 | 26.7 | 19.1 | 7.6 |
| Embodiment 2 | Hβ | 54.0 | 92.6 | 81.6 | 11.0 |
| Embodiment 3 | NaX | 94.5 | 83.2 | 72.1 | 11.1 |
| Embodiment 4 | HX | 96.8 | 76.1 | 64.9 | 11.2 |
| Embodiment 5 | NaY | 91.5 | 96.6 | 76.3 | 20.3 |
| Embodiment 6 | HY | 56.2 | 84.4 | 51.7 | 32.7 |
| Embodiment 7 | HUSY | 91.4 | 90.2 | 73.5 | 16.7 |
| Embodiment 8 | HSSY | 74.5 | 82.0 | 54.8 | 27.2 |
| Embodiment 9 | ZSM-5 | 36.6 | 55.4 | 28.5 | 26.9 |
| Embodiment | ZSM-22 | 46.9 | 88.0 | 78.4 | 9.6 |
| 10 | |||||
| Embodiment 11 | ?ZSM-23 | 27.6 | 79.9 | 73.4 | 6.5 |
| Embodiment 12 | ?SAPO-11 | 78.2 | 67.9 | 50.8 | 17.1 |
| Embodiment 13 | ?CaA | 40.2 | 81.2 | 63.9 | 17.3 |
Embodiment 14
Take by weighing the six water nickelous chlorides of 2.1g, add quantitative distilled water and be configured to nickel chloride solution, and the carrier of dipping 5.0g NaX, in 120 ℃ of oven dry, get nickeliferous carrier; Get 25ml 1.0MKBH
4, contain the aqueous solution of 0.2MNaOH, in ice-water bath with KBH
4The aqueous solution is added drop-wise in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, drip finish after, treat that no hydrogen emits, show that reaction finishes, the solid product that obtains with distilled water wash promptly gets catalyzer provided by the invention to there not being acid group.
Hydrogenolysis of glycyl alcohol system 1,2-propylene glycol are reflected in the Monel autoclave that volume is 600ml carries out.Reactor is used the hydrogen exchange mistake in advance, adds the 40g glycerol then, 120g water, catalyzer 0.5g (by metal).At 200 ℃, 6.0MPa hydrogen reacts under the rotating speed 500rpm condition, and the reaction times is 10 hours.Test result is listed in table 2.
Embodiment 15
Except carrier being changed into SBA-15 type molecular sieve, other step adopts the method for embodiment 14 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 2.
Embodiment 16
Except carrier being changed into MCM-41 type molecular sieve, other step adopts the method for embodiment 14 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 2.
The hydrogenolysis of glycyl alcohol performance of table 2 embodiment 14～16 each catalyzer
| Example number | Molecular sieve type | Transformation efficiency % | The overall selectivity % of primary product | Primary product distribution % | |
| 1, the 2-propylene glycol | Ethylene glycol | ||||
| 14 | ?NaX | 44.7 | 80.0 | 68.6 | ?11.4 |
| 15 | ?SBA-15 | 12.6 | 69.5 | 69.5 | ?- |
| 16 | ?MCM-41 | 20.5 | 74.9 | 63.7 | ?11.2 |
Embodiment 17～21
NiB/NaX catalyzer to different loadings under the reaction conditions identical with example 1 has carried out glycerol hydrocracking experiment, and it the results are shown in table 3.
The glycerol catalytic hydrogenolysis system 1 of the NiB/NaX catalyzer of the different loadings of table 3,2-propylene glycol performance
| Example number | Catalyzer | Transformation efficiency % | The overall selectivity % of primary product | Primary product distribution % | |
| 1, the 2-propylene glycol | Ethylene glycol | ||||
| 17 | NiB/NaX(2.8wt％Ni) | 28.1 | 85.7 | 72.1 | 13.6 |
| 18 | NiB/NaX(4.5wt％Ni) | 50.8 | 90.0 | 77.3 | 12.7 |
| 19 | NiB/NaX(6.8wt％Ni) | 85.0 | 75.3 | 62.8 | 12.5 |
| 20 | NiB/NaX(8.2wt％Ni) | 86.0 | 84.1 | 72.2 | 11.9 |
| 21 | NiB/NaX(11.3wt％Ni) | 97.6 | 53.1 | 49.5 | 3.6 |
Embodiment 22～26
The explanation of this example is by cationic exchange modulation NaX acidic zeolite, and the glycerol hydrocracking performance of the molecular sieve catalyst of different exchange degrees.
The NH of configuration 1M
4NO
3Solution is pressed 100g NaX molecular sieve: 1000mlNH
4NO
3Solution proportion mixed molecular sieve and exchange solution.Exchange is 3 hours under stirring in 80 ℃ of waters bath with thermostatic control, filters the back with deionized water wash 3 times, and the sample after the washing repeats aforesaid method and exchanges 3 times again.The final sample that obtains in 550 ℃ of following roastings of retort furnace, obtains the HX molecular sieve carrier through washing, oven dry.
The NaNO of configuration 1M
3Solution carries out Na with same ratio and method to NaX
+Exchange and roasting.The sample that exchanges 2 acquisitions is the NaX-2 molecular sieve carrier.The sample that exchanges 4 acquisitions is the NaX-4 molecular sieve carrier.
The KNO of configuration 1M
3Solution with same ratio and method, carries out K to NaX
+Exchange and roasting.The sample that exchanges 4 acquisitions is the KX-4 molecular sieve carrier.
Adopt the method identical to prepare catalyzer to prepared sieve sample, under the reaction conditions identical, estimated hydrogenolysis of glycyl alcohol system 1 with embodiment 1 with embodiment 1 by different cationic exchange, the performance of 2-propylene glycol, it the results are shown in table 5.
The reactivity worth of five kinds of catalyzer of table 5
| Example number | Catalyzer | Transformation efficiency % | The overall selectivity % of primary product | Primary product distribution % | |
| 1, the 2-propylene glycol | Ethylene glycol | ||||
| 22 | NiB/HX | 96.8 | 76.1 | 64.9 | 11.2 |
| 23 | NiB/NaX | 94.5 | 83.2 | 72.1 | 11.1 |
| 24 | NiB/NaX-2 | 86.6 | 94.6 | 80.4 | 14.2 |
| 25 | NiB/NaX-4 | 79.8 | 82.6 | 72.1 | 10.5 |
| 26 | NiB/KX-4 | 69.6 | 88.5 | 75.5 | 13.0 |
Embodiment 27
Except changing six water nickelous chloride amounts into 2.0g, 1.0MKBH
4The volume that contains the aqueous solution of 0.2MNaOH changes into outside the 25ml, and other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 6.
Embodiment 28
Except changing six water nickelous chloride amounts into 4.1g, 1.0MKBH
4The volume that contains the aqueous solution of 0.2MNaOH changes into outside the 50ml, and other step adopts the method for embodiment 1 to carry out, and gets catalyzer provided by the invention.Test result is listed in table 6.Table 6 catalyst levels is to the hydrogenolysis of glycyl alcohol Effect on Performance
| Example number | Catalyzer | Transformation efficiency % | The overall selectivity % of primary product | Primary product distribution % | |
| 1, the 2-propylene glycol | Ethylene glycol | ||||
| 27 | NiB/NaX | 44.7 | 80.0 | 68.6 | 11.4 |
| 28 | NiB/NaX | 71.2 | 72.5 | 61.5 | 11.0 |
| 2 | NiB/NaX | 94.5 | 83.2 | 72.1 | 11.1 |
Claims (9)
1. the application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol, it is characterized in that: catalyzer is to be main active component with Ni, the carrier that adopts is Si-Al molecular sieve, mesopore molecular sieve or phosphate aluminium molecular sieve, and the content of active ingredient Ni in catalyzer is 1～25wt%; Also be added with boron in the described catalyzer as auxiliary agent, wherein the mol ratio of boron and nickel is 1.0～10.0; This catalyzer is used for hydrogenolysis of glycyl alcohol prepared in reaction 1, and 2-propylene glycol and ethylene glycol can be realized the high-activity high-selectivity hydrocracking of glycerol.
2. according to the described application of claim 1, it is characterized in that:
Described Si-Al molecular sieve is beta-molecular sieve, X type molecular sieve, Y zeolite or the mordenite with twelve-ring pore passage structure, ZSM-5, the ZSM-22 or the ZSM-23 that perhaps have the ten-ring pore passage structure perhaps have the A type molecular sieve of octatomic ring pore passage structure;
Described mesopore molecular sieve is MCM41 or SBA-15;
Described phosphate aluminium molecular sieve is SAPO-11.
3. according to the described application of claim 1, it is characterized in that: described carrier is X or the Y zeolite with octahedral zeolite cage twelve-ring structure.
4. according to the described application of claim 1, it is characterized in that: described carrier is the mixture of H type, Na type or H type and Na type.
5. according to the described application of claim 1, it is characterized in that:
Described catalyzer adopts the method preparation of dipping,
1) takes by weighing the soluble nickel salt impregnating porous carrier solution in proportion, in 100～130 ℃ of oven dry;
2) activation of catalyzer: in-5～100 ℃ scope, under alkaline condition, is the BH that contains of 0.1～10.0M with volumetric molar concentration with nickeliferous porous support
4 -Solution drip, fully stir and carry out reduction reaction, generate black solid, what dripped contains BH
4 -Solution and the mol ratio of nickel salt be 1.0～10.0; The black solid that obtains is washed with distilled water to neutrality, makes loaded catalyst.
6. according to the described application of claim 5, it is characterized in that: described nickel salt solution refers to the aqueous solution of nickel salt, and described nickel salt is selected from one or more in nickelous chloride, single nickel salt, nickel acetate, the nickelous nitrate.
7. according to the described application of claim 5, it is characterized in that: the described BH of containing
4 -Solution be BH
4 -The aqueous solution, described BH
4 -Precursor be selected from a kind of in sodium borohydride, the POTASSIUM BOROHYDRIDE, perhaps select both mixtures.
8. according to the described application of claim 5, it is characterized in that: described reductive condition under alkaline condition, is the contain BH of 0.2～2.0M with volumetric molar concentration at 0～40 ℃
4 -Solution reduction; What dripped contains BH
4 -Solution and the mol ratio of nickel salt be preferably 1.0～6.0.
9. according to the described application of claim 1, it is characterized in that: in the presence of the described catalyzer of claim 1, at 100～300 ℃, 1.0 under～10.0MPa the hydrogen pressure, with water is solvent, carry out the hydrogenolysis of glycyl alcohol reaction, prepared catalyzer is to 1, and 2-propylene glycol and ethylene glycol have very high selectivity and yield.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100127093A CN101381280B (en) | 2007-09-05 | 2007-09-05 | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100127093A CN101381280B (en) | 2007-09-05 | 2007-09-05 | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381280A CN101381280A (en) | 2009-03-11 |
| CN101381280B true CN101381280B (en) | 2011-12-21 |
Family
ID=40461362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100127093A Expired - Fee Related CN101381280B (en) | 2007-09-05 | 2007-09-05 | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101381280B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019185B (en) * | 2009-09-16 | 2012-12-05 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in hydrocracking reaction of xylitol |
| CN102241405A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院过程工程研究所 | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method |
| CN103159587A (en) * | 2011-12-08 | 2013-06-19 | 中国科学院大连化学物理研究所 | Application for catalyst in hydrocracking for biological polyol |
| CN102557872B (en) * | 2011-12-19 | 2016-05-04 | 东南大学 | A kind of method of preparing propanediol through one-step glycerol hydrogenolysis |
| WO2014081951A1 (en) | 2012-11-21 | 2014-05-30 | University Of Tennesee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN103922893B (en) * | 2014-04-19 | 2015-11-25 | 青岛科技大学 | A kind of composite catalyst hydrogenolysis catalysis of glycerin prepares the method for 1,2-PD |
| CN105669373B (en) * | 2014-11-17 | 2017-09-15 | 中国科学院大连化学物理研究所 | A kind of method of polyalcohol hydrogenolysis |
| CN108212200A (en) * | 2016-12-14 | 2018-06-29 | 天津大学（青岛）海洋工程研究院有限公司 | A kind of preparation method of lignin-base phenols aqueous phase reforming catalyst for preparing hydrogen |
| CN112058304B (en) * | 2019-11-20 | 2023-04-25 | 榆林学院 | Dual-function catalyst capable of adjusting solid acidity, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264356A (en) * | 1997-07-23 | 2000-08-23 | 国际壳牌研究有限公司 | Hydrogenolysis of glycerol |
| WO2003035582A1 (en) * | 2001-10-23 | 2003-05-01 | Battelle Memorial Institute | Hydrogenolysis of 6-carbon sugars and other organic compounds |
| WO2007067426A1 (en) * | 2005-12-08 | 2007-06-14 | Sud-Chemie Inc. | Catalyst for the production of polyols by hydrogenolysis of carbohydrates |
-
2007
- 2007-09-05 CN CN2007100127093A patent/CN101381280B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264356A (en) * | 1997-07-23 | 2000-08-23 | 国际壳牌研究有限公司 | Hydrogenolysis of glycerol |
| WO2003035582A1 (en) * | 2001-10-23 | 2003-05-01 | Battelle Memorial Institute | Hydrogenolysis of 6-carbon sugars and other organic compounds |
| WO2007067426A1 (en) * | 2005-12-08 | 2007-06-14 | Sud-Chemie Inc. | Catalyst for the production of polyols by hydrogenolysis of carbohydrates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101381280A (en) | 2009-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101381280B (en) | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol | |
| CN102091624B (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| CN101596465A (en) | Based on metallic catalyst of metal-organic framework and its production and application | |
| CN101497047B (en) | Application of X-type molecular sieve supported Ni-based catalyst in hydrogenolysis of glycyl alcohol | |
| CN110961110B (en) | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination | |
| CN102489315A (en) | Ruthenium catalyst, preparation method and application in synthesizing tetrahydrofurfuryl alcohol | |
| CN104588011A (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN108499566A (en) | A kind of preparation method and application of CuNi bases catalyst | |
| CN106866364A (en) | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol | |
| CN102319575B (en) | Application of Cu-Fe-based catalyst in synthesis of higher alcohol with synthetic gas | |
| CN104072335B (en) | A kind of cellulose catalytic converts dihydroxylic alcohols processed, hexahydroxylic alcohols and the method for gamma-valerolactone | |
| CN103030527A (en) | Method for producing isopropanol through acetone solution hydrogenation | |
| CN110479348A (en) | A kind of preparation method and applications of the monatomic catalyst of metal | |
| CN104230641B (en) | Produce the method for isopropyl benzene | |
| CN102794178A (en) | Selective hydrogenation catalyst and preparation thereof | |
| CN102557872B (en) | A kind of method of preparing propanediol through one-step glycerol hydrogenolysis | |
| CN102389800A (en) | Catalyst for use in preparation of 1,2-propanediol by low-temperature low-pressure hydrogenation of biological glycerol and preparation method thereof | |
| CN1318140C (en) | Catalyst for synthesizing low carbon mixed alcohol by synthetic gas and its preparation method | |
| CN104741148A (en) | Method for preparing 3-chlorine-4 fluoronitrobenzene hydrogenation catalyst | |
| CN102600849B (en) | Methanol cracking catalyst for methanol-gasoline dual-fuel automobiles and preparation and application thereof | |
| CN101434551A (en) | Method for synthesizing monoethanolamine | |
| CN112138676A (en) | Catalyst for preparing o-phenylphenol and preparation method thereof | |
| CN111420657A (en) | Ru-based catalyst for synthesizing 3-pentanone through ethylene conversion and preparation method and application thereof | |
| CN109364923A (en) | Copper-based water-fast catalyst M-Cu/SiO2Preparation method and application method | |
| CN101301624A (en) | Al2O3-HZSM-5 compound solid acid catalyst prepared by chemical precipitation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111221 Termination date: 20180905 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |