CN106905109A - A kind of method that catalytic hydrogenolysis cellulose produces propane diols - Google Patents
A kind of method that catalytic hydrogenolysis cellulose produces propane diols Download PDFInfo
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- CN106905109A CN106905109A CN201710034066.6A CN201710034066A CN106905109A CN 106905109 A CN106905109 A CN 106905109A CN 201710034066 A CN201710034066 A CN 201710034066A CN 106905109 A CN106905109 A CN 106905109A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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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
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method that catalyst hydro-thermal hydrogenolysis cellulose produces propane diols, concretely comprise the following steps：Microcrystalline cellulose and catalyst by proportion are added in reactor, are 210 DEG C 240 DEG C in reaction temperature, the reaction time is 15min 45min, 5MPa 7MPa H2Hydro-thermal reaction is carried out under conditions of pressure, it is the catalyst with beta-molecular sieve as carrier to react the catalyst.Metallic carrier is W metal and WO3.It is easy to operate the present invention relates to technique simplicity, and non-secondary pollution, compared with the ethylene glycol industrial production that existing ethene is reaction raw materials, changing waste into resources utilization is realized, it is provided simultaneously with certain economic and social profit.
Description
Technical field
The present invention relates to a kind of method that catalytic hydrogenolysis cellulose produces propane diols, particularly a kind of is to reduce with cheap metal
Agent and the hydrothermal reduction method of catalyst, belong to environment chemical engineering field.
Background technology
In recent years, the increasingly depleted of fossil resource, the continuous growth of energy demand and global climate and environment it is continuous
Deteriorate, force the mankind to have to find the renewable new energy that can substitute fossil resource, wherein, most possible substitute fossil fuels
Be the biomass for being called " green coal ".Biomass energy because its have rich reserves, recyclability, neutral carbon, can be again
The good environmental effect such as natural disposition, pollution-free is just increasingly subject to pay attention to and developed rapidly, and wherein cellulose is biomass
The most abundant constituent of middle content, is the initiation material of derived energy chemical, there is very big development prospect.
Propane diols in polyalcohol is the important industrial chemicals of a class, be widely used in production polyester fiber (terylene) and
The industries such as antifreezing agent, it is contemplated that in following decades, its demand will be multiplied.At present, it is industrial mainly by oil second
Alkene and oil propylene oxirane are obtained with the hydration of expoxy propane, i.e., obtain the alkene of corresponding carbon number from oil first,
Then epoxyalkane is obtained by epoxidation again, last epoxyalkane obtains propane diols by hydration reaction.Therefore using biological
Matter base cellulose can reduce for raw material carrys out synthesizing propanediol and fossil resources are depended on unduly, and reduce CO2Discharge, this
Process will have Atom economy very high, meet the requirement of Green Chemistry.The economic worth of low-carbon polyol is also very huge
Greatly, if the price of ethylene glycol is 660 beautiful yuan/ton, the price of propane diols is 1500 beautiful yuan/ton.Therefore, cellulose how is improved to turn
Economic worth low-carbon polyol higher is turned to efficient most important using biomass energy.
The content of the invention
It is an object of the invention to provide a kind of method that catalytic hydrogenolysis cellulose produces propane diols, realize that cellulose is converted into height
Added value propane diols.
To solve above-mentioned technical problem, the present invention is achieved through the following technical solutions：
The method that catalytic hydrogenolysis cellulose proposed by the present invention produces propane diols, comprises the following steps that：
（1）Catalyst synthesizes
（1.1）First take 0.15-0.25g phosphotungstic acids（H3O10W12·12H2O）It is soluble in water, solution is then slowly dropped to 1g β
Molecular sieve gets on, ultrasonic 30min, stands aging 12h, then dries 4h at 110 DEG C, is then calcined 4h at 550 DEG C；
（1.2）Take the water nickel nitrates of 0.25-0.75g six（Ni(NO3)2·6H2O）It is soluble in water, solution is then slowly dropped to step
Suddenly（1.1）The material of synthesis gets on, ultrasonic 30min, stands aging 12h, then dries 4h at 110 DEG C, then in 550 DEG C of roastings
4h；
（1.3）By step（1.2）Resulting materials reduce 4h in 550 DEG C of hydrogen stream；Obtain Ni-W/ beta catalysts；
Wherein：Phosphotungstic acid, the ratio that adds of six water nickel nitrates are 15:5-5:25；
（2）Catalytic reaction
Take step（1.3）The Ni-W/ beta catalysts of synthesis, cellulose and water are placed in the jar of Teflon, are subsequently placed in high temperature high
In pressure reactor, in 210-240 DEG C of reaction temperature, reaction time 15-45min enters water-filling under conditions of reaction pressure 5-7MPa
Thermal reduction reaction, cellulose aqueous solution is reduced to the small organic molecule mixed liquor based on propane diols, then purifies and separates,
Obtain propane diols；Wherein：Catalyst amount is 5 mmol/L-15 mmol/L.
In the present invention, cellulose is primary product for the propane diols of substrate.
The beneficial effects of the invention are as follows:
1 raw material of the invention is the cellulose that nature is widely present and does not utilize effectively（Such as agricultural crop straw）, it comes
Source is extensive, with low raw-material cost advantage.Biomass resource is utilized relative to others（Such as starch, glucose）Production third
The technology of glycol, eliminates the harmful effect that biomass energy conversion process may be caused to the grain security of the mankind
The reducing agent that 2 present invention are used is cheap and easy to get, and catalyst is equally easily obtained, and price is also relatively cheap.
3 present invention can be completed by single step reaction, and process is simple is easy to operate.
4 present invention can solve the problem that the handling problems of biological diesel oil byproduct glycerin, and the propane diols for producing can be used for
Industry, realizes the target of changing waste into resources.
5., using Degradation and Transformation cellulose is hydrogenated with hydrothermal condition, reaction system is environment-friendly, pollution-free.It is reaction with water
Medium, any inorganic acid alkali is not used in reaction, avoid common problem of environmental pollution in cellulose degradation technique.
6. course of reaction of the present invention is simple, without carrying out sour water solution to cellulose in advance, only by needing to raw material
Carry out physics levigate all right.
Brief description of the drawings Fig. 1 schemes for the TEM of catalyst；Wherein：A, the TEM shape appearance figures under the nm scales of catalyst 200, b is urged
TEM shape appearance figures under the nm scales of agent 100, c, the TEM shape appearance figures under the nm scales of catalyst 50, d, the nm scales of catalyst 20
Under TEM shape appearance figures；
Fig. 2 is the XRD analysis figure of catalyst.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Equi-volume impregnating prepares bimetallic catalyst step：
（1）Take 0.2g phosphotungstic acids（H3O10W12·12H2O）It is dissolved in 1.2 mL water, is stirred with clean glass bar, places into super
The absorption situation of the active beta-molecular sieve of ultrasonic 30 min or so observations in sound instrument, if absorption is uneven, continues ultrasound, and absorption is good
Aging 12 h, is placed into baking oven afterwards, and 4 h are dried under conditions of 110 DEG C, is put into chamber type electric resistance furnace after being cooled to room temperature,
4 h are calcined under conditions of 550 DEG C.
（2）Take the water nickel nitrates of 0.35g six（Ni(NO3)2·6H2O）It is dissolved in 1.2ml water, is added to step（1）It is roasting
Material in, and repeat ultrasound, it is aging, dry and roasting process.Finally, the catalyst after roasting is used in tube furnace
5% hydrogen and 95% nitrogen mixture hydrogenate 4 h under the conditions of 500 DEG C.The catalyst prepared by this kind of method is designated as：7%
Ni-20%W/β。
Accompanying drawing 1 is the bimetallic 7%Ni-20%W/ beta catalysts of the preparation of embodiment 1 in 200 nm, 100 nm, 50 nm, 20
TEM shape appearance figures under nm scales.
Cellulose catalytic conversion process：Cellulose is being vacuum dried 12 h using preceding by 105 DEG C.Cellulose catalytic hydrogenolysis
Reaction is carried out in stainless steel cauldron.1g celluloses, 0.3 g catalyst and 40 mL distilled water are sequentially added into Teflon
In container tank, Teflon container tank is put into stainless steel cauldron again then；H will be filled with reaction vessel2H is first used before2Put
Air three times or so in reactor are changed, Stress control is in 6 MPa；Reactor is put into heating stirring controller and inserts thermocouple
Heat temperature raising, and stirred with the speed of 1000 r/min, when reaction temperature reaches 240 DEG C of beginning timing of design temperature, reaction 30
Heater is closed after min.After reaction terminates, reactor is cooled to room temperature, is separated by filtration product after release pressure, fiber
Plain conversion ratio is 100%, and the yield of propane diols reaches 19.3%.
Embodiment 2
Under Ni-W collective effects, the solid residue collected after being reacted in embodiment 1 is clean with deionized water filtration and washing,
70 DEG C of drying in oven is to be measured.Detected using type x ray diffractometer x, 2 θ angular regions of x ray diffraction are 5-80o, corner
Speed is 10o/min, and analysis result shows as shown in Figure 2, and the material that catalytic action is played in catalyst is simple substance Ni and WO3,
Nickel tungstate（NiWO4）Generation hinder the degraded of cellulose and the generation of polyalcohol.
Embodiment 3
As different from Example 1：The quality of phosphotungstic acid used is 0.15 g, the synthesis step of remaining catalyst, cellulose
Catalytic degradation process is same as Example 1.7%Ni-15%W/ beta catalysts degraded cellulose obtained in the embodiment produces propane diols
Yield be 15.8%, cellulose conversion ratio be 100%.
Embodiment 4
As different from Example 1：The quality of phosphotungstic acid used is 0.25 g, the synthesis step of remaining catalyst, cellulose
Catalytic degradation process is same as Example 1.7%Ni-25%W/ beta catalysts degraded cellulose obtained in the embodiment produces propane diols
Yield be 7.2%, cellulose conversion ratio be 92%.
Embodiment 5
As different from Example 1：Six water nickel nitrate used（Ni(NO3)2·6H2O）Quality be 0.25 g, remaining catalyst
Synthesis step, cellulose catalytic degradation process it is same as Example 1.5%Ni-20%W/ β catalysis obtained in the embodiment
The yield that agent degraded cellulose produces propane diols is 15.8%, and cellulose conversion ratio is 100%.
Embodiment 6
As different from Example 1：Six water nickel nitrate used（Ni(NO3)2·6H2O）Quality be 0.45 g, remaining catalyst
Synthesis step, cellulose catalytic degradation process it is same as Example 1.9%Ni-20%W/ β catalysis obtained in the embodiment
The yield that agent degraded cellulose produces propane diols is 18.7%, and cellulose conversion ratio is 100%.
Embodiment 7
As different from Example 1：Six water nickel nitrate used（Ni(NO3)2·6H2O）Quality be 0.75 g, remaining catalyst
Synthesis step, cellulose catalytic degradation process it is same as Example 1.15%Ni-20%W/ β catalysis obtained in the embodiment
The yield that agent degraded cellulose produces propane diols is 3.6%, and cellulose conversion ratio is 89%.
Embodiment 8
As different from Example 1：Reaction temperature is adjusted to 210 DEG C, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.Embodiment 7%Ni-20%W/ beta catalysts degraded cellulose produce propane diols yield be
16.6%, cellulose conversion ratio is 100%.
Embodiment 9
As different from Example 1：Reaction temperature is adjusted to 270 DEG C, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield that the embodiment cellulose produces propane diols is 17.1%, and cellulose conversion ratio is 100%.
Embodiment 10
As different from Example 1：Reaction time is adjusted to 15 min, the synthesis step of catalyst, remaining cellulose catalytic
Degradation process is same as Example 1.The yield that the embodiment cellulose produces propane diols is 4.4%, and cellulose conversion ratio is 77%.
Embodiment 11
As different from Example 1：Reaction time is adjusted to 60min, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield that the embodiment cellulose produces propane diols is 18.6%, and cellulose conversion ratio is 100%.
Embodiment 12
As different from Example 1：Reaction pressure is adjusted to 5MPa, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield that the embodiment cellulose produces propane diols is 15.3%, and cellulose conversion ratio is 90%.
Embodiment 13
As different from Example 1：Reaction pressure is adjusted to 7MPa, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield that the embodiment cellulose produces propane diols is 18.9%, and cellulose conversion ratio is 100%.
Embodiment 14
As different from Example 1：The amount of substrate is adjusted to 0.5g, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield of this catalytic reaction propane diols is 17.9%, and cellulose conversion ratio is 100%.
Embodiment 15
As different from Example 1：The amount of substrate is adjusted to 2g, the synthesis step of catalyst, the degraded of remaining cellulose catalytic
Process is same as Example 1.The yield of this catalytic reaction propane diols is 14.9%, and cellulose conversion ratio is 87%.
Embodiment 16
As different from Example 1：Mixing speed is adjusted to 100 r/min, and the synthesis step of catalyst, remaining cellulose are urged
Change degradation process same as Example 1.The yield of this catalytic reaction propane diols is 13.9%, and cellulose conversion ratio is 84%.
Embodiment 17
As different from Example 1：Mixing speed is adjusted to 500 r/min, and the synthesis step of catalyst, remaining cellulose are urged
Change degradation process same as Example 1.The yield of this catalytic reaction propane diols is 16.9%, and cellulose conversion ratio is 97%.
Embodiment 18
As different from Example 1：The consumption of water is adjusted to 20 ml, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield of this catalytic reaction propane diols is 16.3%, and cellulose conversion ratio is 94%.
Embodiment 19
As different from Example 1：The consumption of water is adjusted to 60 ml, the synthesis step of catalyst, remaining cellulose catalytic drop
Solution preocess is same as Example 1.The yield of this catalytic reaction propane diols is 15.3%, and cellulose conversion ratio is 100%.
Embodiment 20
As different from Example 1：Using NaOH, Ca (OH)2、Ba(OH)2Three kinds of ease of solubility highly basic are probed into as base catalyst
Influence of the species and consumption of base catalyst to cellulose degradation.Add three kinds of reaction system cellulose conversions of base catalyst
Rate is 100%.When not strengthening aqueous slkali, 1,2-PG yield is 19.3%, and after adding aqueous slkali, 1,2-PG yield has
Improved.For adding the catalyst system and catalyzing of NaOH solution, the change in concentration of NaOH solution is to 1,2-PG yield incrementss
Less significantly, maximum output is 25.5% for change.For adding the catalyst system and catalyzing of the solution of Ca (OH) 2, compared to NaOH bodies
It is more obvious effect, when the concentration of Ca (OH) 2 is 10 mmol/L, 1,2-PG yield is up to 30.1%.As addition Ba
(OH) during 2 solution, the raising of 1,2-PG yield also than more significant, when adding Ba (OH) 2 solution of 10 mmol/L, 1,2-PG
Yield reaches 32.5%.
Embodiment 21
As different from Example 20：Employ glucose has carried out a series of base catalyzed reactions as substrate.
Embodiment 22
The recycling performance of catalyst is probed into using 7Ni-20W/ beta-molecular sieve catalyst system and catalyzings.Each time after reuse, will be remaining
Solid catalyst carries out the cleaning of centrifugation deionized water repeatedly up to eluent is neutrality, is carried out down after the solid drying after centrifugation
Reuse.1,2-PD yield drops to 31.6% after second reuse is carried out from 32.5%, and in third time reuse
After drop to 28.6%, the conversion ratio of cellulose is respectively 96% and 92% in the case of two kinds, meanwhile, product changes in distribution is simultaneously failed to understand
It is aobvious.
Claims (1)
1. a kind of method that catalytic hydrogenolysis cellulose produces propane diols, it is characterised in that comprise the following steps that：
（1）Catalyst synthesizes
（1.1）First take 0.15-0.25g phosphotungstic acids（H3O10W12·12H2O）It is soluble in water, solution is then slowly dropped to 1g β
Molecular sieve gets on, ultrasonic 30min, stands aging 12h, then dries 4h at 110 DEG C, is then calcined 4h at 550 DEG C；
（1.2）Take the water nickel nitrates of 0.25-0.75g six（Ni(NO3)2·6H2O）It is soluble in water, solution is then slowly dropped to step
Suddenly（1.1）The material of synthesis gets on, ultrasonic 30min, stands aging 12h, then dries 4h at 110 DEG C, then in 550 DEG C of roastings
4h；
（1.3）By step（1.2）Resulting materials reduce 4h in 550 DEG C of hydrogen stream；Obtain Ni-W/ beta catalysts；
Wherein：The ratio that adds of Ni-W is 15:5-5:25；
（2）Catalytic reaction
Take step（1.3）The Ni-W/ beta catalysts of synthesis, cellulose and water are placed in the jar of Teflon, are subsequently placed in high temperature high
In pressure reactor, in 210-240 DEG C of reaction temperature, reaction time 15-45min enters water-filling under conditions of reaction pressure 5-7MPa
Thermal reduction reaction, cellulose aqueous solution is reduced to the small organic molecule mixed liquor based on propane diols, then purifies and separates,
Obtain propane diols；Wherein：Catalyst amount is 5 mmol/L-15 mmol/L.
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| CN201710034066.6A CN106905109A (en) | 2017-01-18 | 2017-01-18 | A kind of method that catalytic hydrogenolysis cellulose produces propane diols |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573213A (en) * | 2017-08-11 | 2018-01-12 | 厦门大学 | A kind of chemical method of biomass ethanol and ethylene glycol |
| CN107971035A (en) * | 2017-11-23 | 2018-05-01 | 黑龙江省能源环境研究院 | A kind of method that straw base cellulose chemistry conversion prepares polyalcohol |
| CN115636720A (en) * | 2022-11-01 | 2023-01-24 | 同济大学 | Method for producing 1, 2-propylene glycol by one-step method catalysis biomass |
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| CA2973436A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate |
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| CA2973436A1 (en) * | 2015-01-13 | 2016-07-21 | Avantium Knowledge Centre B.V. | Process for preparing ethylene glycol from a carbohydrate |
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| NEGOI A 等: "The hydrolytic hydrogenation of cellulose to sorbitol over", 《CATALYSIS TODAY》 * |
| 曹月领等: "Ni-WO3/SBA-15催化剂上纤维素的水解加氢", 《燃料化学学报》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573213A (en) * | 2017-08-11 | 2018-01-12 | 厦门大学 | A kind of chemical method of biomass ethanol and ethylene glycol |
| CN107971035A (en) * | 2017-11-23 | 2018-05-01 | 黑龙江省能源环境研究院 | A kind of method that straw base cellulose chemistry conversion prepares polyalcohol |
| CN115636720A (en) * | 2022-11-01 | 2023-01-24 | 同济大学 | Method for producing 1, 2-propylene glycol by one-step method catalysis biomass |
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