CN104998644B - Hydrothermal liquefaction produces catalyst of bio-oil and preparation method and application - Google Patents
Hydrothermal liquefaction produces catalyst of bio-oil and preparation method and application Download PDFInfo
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- CN104998644B CN104998644B CN201410155539.4A CN201410155539A CN104998644B CN 104998644 B CN104998644 B CN 104998644B CN 201410155539 A CN201410155539 A CN 201410155539A CN 104998644 B CN104998644 B CN 104998644B
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Abstract
The invention discloses catalyst of a kind of catalytically liquefying biomass oil and preparation method and application.The catalyst is made up of carrier and the metal oxide being carried on the carrier；Wherein, the material for constituting carrier is clay mineral powder；Metallic element in the metal oxide is selected from least one of group VIII metallic element；In the carbon monoxide-olefin polymeric, the mass percentage content of metal oxide is 2% 4%.The catalyst has the advantage for the bio-oil yield that is significantly improved, the calorific value average out to 32.46MJ/kg of bio-oil, while relatively stable.
Description
Technical field
The present invention relates to biomass engineering and energy field, the more particularly to catalyst of catalytically liquefying biomass oil and preparation
Method and application.
Background technology
With in world wide energy resource consumption be continuously increased and energy security situation continuous deterioration, biomass energy
Gradually get the attention, especially in recent decades, the demand to biomass energy increases sharply.In numerous biomass
In raw material, microalgae is because of its higher photosynthetic efficiency, and growth rate and yield per unit area are considered as the life of great prospect
Raw material of substance.In addition, in fresh water and salt solution, microalgae can large-scale culture, be not take up arable land and Environmental sensitive area.Cause
This, the microalgae biomass energy is considered as third generation biomass energy.
The content of the invention
It is an object of the invention to provide a kind of catalyst of catalytically liquefying biomass oil and preparation method and application.
The catalyst that the present invention is provided, is made up of carrier and the metal oxide being carried on the carrier；
Wherein, the material for constituting the carrier is clay mineral powder；
Metallic element in the metal oxide is selected from least one of group VIII metallic element.
In the carbon monoxide-olefin polymeric, the mass percentage content of metal oxide is 2%-4%, specially 3%, 2-3% or
3-4%。
In the carrier, the mesh number of clay mineral powder is the mesh of 200 mesh -300, specially 300 mesh；
The clay mineral powder is specially calcite powder；
The metal oxide is NiO.
The method that what the present invention was provided prepare the carbon monoxide-olefin polymeric, comprises the following steps：
1）Drying, roasting, obtain the carrier after foregoing clay mineral powder and binding agent are mixed；
2）With the solution impregnation steps 1 containing group VIII metallic element）Resulting vehicle, then by the carrier drying after dipping
And roasting, obtain the carbon monoxide-olefin polymeric.
The step 1 of the above method）In, the binding agent is polyvinyl alcohol or A.S glue；The polyvinyl alcohol is specially
PVA1788, its average degree of polymerization is 1700-1850, is purchased from Dongguan City Hong Chun trade Co., Ltds；The A.S glue namely oxygen
Change Alumina gel, Zibo Jin Qi Chemical Industry Science Co., Ltd, model LA-25 types can be purchased from；
The mass ratio of clay mineral powder and binding agent is 75：1-2；
In baking step, temperature is 200 DEG C -300 DEG C；Time is 4-8 hours；
The drying is specifically carried out under the following conditions：Dried at 200 DEG C -300 DEG C or 200 DEG C or 250 DEG C or 300 DEG C
It is dry -8 hours 4 hours or 4 hours or 6 hours or 8 hours；
In the calcination stepses, the atmosphere of roasting is air atmosphere；Heating rate is 200 DEG C/h -300 DEG C/h；
Final temperature is 900 DEG C -1000 DEG C, specially 950 DEG C, 900-950 DEG C or 950-1000 DEG C；
The time of roasting is 2-4 hours；
The roasting is specifically carried out under the following conditions：In air atmosphere, with 200 DEG C/h -300 DEG C/h or
200 DEG C/h or 300 DEG C/h rise to 900 DEG C -1000 DEG C or 900 DEG C or 950 DEG C or 1000 DEG C, constant temperature calcining 2 hours -4
Hour or 2 hours or 4 hours；
Methods described also includes：In step 1）After mixing step, before baking step, by clay mineral powder and bonding
Agent is squeezed into a diameter of 1mm circle bar shaped with squeezer；
The step 2）In impregnation steps, group VIII metallic element is nickel；The method of dipping is specially that will contain
The solution of group VIII metal element is uniformly sprayed on step 1）In resulting vehicle.
In the solution containing group VIII metallic element, the concentration of group VIII metallic element is 2.0g/100ml-
4.0g/100ml, specially 2.0g/100ml-4.0g/100ml or 2.0g/100ml or 3.0g/100ml or 4.0g/100ml；Institute
The concentration of group VIII metallic element is stated with the densimeter of metal oxide；
In the drying steps, temperature is 100 DEG C -150 DEG C, and the time is -6 hours 2 hours；
The drying is specifically carried out under the following conditions：Done at 100 DEG C -150 DEG C or 100 DEG C or 125 DEG C or 150 DEG C
Dry -6 hours 2 hours or 2 hours or 4 hours or 6 hours；
In the calcination stepses, the atmosphere of roasting is vacuum atmosphere, and vacuum is 0.01MPa-0.02MPa；Heating rate
For 100 DEG C/h -200 DEG C/h；
Final temperature is 500 DEG C -600 DEG C, specially 550,500-550 or 550-600 DEG C；
The time of roasting is 1-4 hours, specially 2 or 2-4 hours；
The roasting is specifically carried out under the following conditions：With 100 DEG C/h -200 DEG C/h or 100 DEG C/h or
150 DEG C/h or 200 DEG C/h rise to 500 DEG C -600 DEG C or 500 DEG C or 550 DEG C or 600 DEG C, and constant temperature calcining 1 hour -4 is small
When or 1 hour or 2 hours or or 1-2 hours or 2-4 hours；
In addition, application of the carbon monoxide-olefin polymeric of the invention described above offer in bio-oil quality is improved, falls within this
The protection domain of invention；Wherein, the raising bio-oil quality is selected from following at least one：
1）Improve the yield of bio-oil；
2）Improve the hydrogen content in bio-oil；
3）Reduce the phosphorus content in bio-oil；
4）Reduce the nitrogen content in bio-oil.
Application of the carbon monoxide-olefin polymeric that the invention described above is provided in bio-oil is prepared, falls within the protection of the present invention
Scope；
Present invention also offers a kind of method for preparing bio-oil, this method comprises the following steps：In the catalyst
In the presence of under conditions of, raw material microalgae powder and deionized water are mixed into row hydrothermal liquefaction, the bio-oil is obtained.
In the above method, the consumption of catalyst is the 5%-20% of microalgae powder quality, specially 10%；
The mass ratio of the microalgae powder and water is 1：3-4；
In the hydrothermal liquefaction step, temperature is 200 DEG C -300 DEG C, specially 230 DEG C；
Time is -120 minutes 30 minutes, specially 30 minutes.
The catalyst prepared by the method for the present invention carries out hydrothermal liquefaction reaction, product oil to raw material microalgae powder
Amount is obviously improved, good catalytic activity.The catalyst of catalytically liquefying biomass oil provided by the present invention, in microalgae hydro-thermal liquid
Change in the reaction for producing bio-oil, with reaction condition is alleviated, improve the advantage of product oil yield, the calorific value of bio-oil is put down
32.46MJ/kg is reached, while relatively stable.
Brief description of the drawings
Fig. 1 is experiment process figure.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed.
Embodiment 1, the catalyst for preparing catalytically liquefying biomass oil
1）Calcite is dried, mechanical crushing, with the sieving shakeout removal of impurities of 300 mesh sieve, obtain calcite powder；
Distilled water is heated to boiling, 10g bonding agent polyvinyl alcohol is added into boiling water（PVA1788, average degree of polymerization is
1700-1850, purchased from Dongguan City Hong Chun trade Co., Ltds）, stirring makes after it is completely dissolved, to add 750g calcite in powder
The mass ratio of end, calcite powder and polyvinyl alcohol is 75：1, make calcite powder formation plasticity solid, then pass through extruding
Device, is squeezed into a diameter of 1mm circles bar shaped, dries 4 hours, after temperature is reduced to room temperature, then be placed under the conditions of 200 DEG C
In air atmosphere, 900 DEG C are risen to 200 DEG C/h, constant temperature calcining 2 hours obtains carrier；
2）Nickel nitrate 43g is weighed, is placed in the ammoniacal liquor that mass percentage concentration is 35% and is stirred untill without insoluble matter,
Obtain nickel element and co-impregnated solution of the concentration as 2.0g/100ml is counted using NiO.
With step 2）Gained co-impregnated solution 100ml is uniformly sprayed on step 1）Impregnated on resulting vehicle 100g, and constantly
Upset is shaken up, then the carrier after dipping is placed in into drying 2 hours at 100 DEG C, after temperature is down to room temperature, is risen with 100 DEG C/h
Temperature is to 500 DEG C, constant temperature calcining（Vacuum is 0.01MPa）2 hours, catalyst is obtained, numbering is catalyst A.
Catalyst A is made up of calcite powder and the NiO being carried on carrier, wherein, NiO weight/mass percentage composition is
2%。
Embodiment 2, the catalyst for preparing catalytically liquefying biomass oil
1）Calcite is dried, mechanical crushing, with the sieving shakeout removal of impurities of 300 mesh sieve, obtain calcite powder；
Distilled water is heated to boiling, 20g adhesive A .S glue is added into waste water（Being purchased from the golden fine jade chemical science and technology in Zibo has
Limit company, model LA-25 types）, stirring makes after it is completely dissolved, and adds 750g calcite powder, calcite powder with it is poly-
The mass ratio of vinyl alcohol is 75：2, make calcite powder formation plasticity solid, then by squeezer, be squeezed into a diameter of
1mm justifies bar shaped, dries 6 hours, after temperature is reduced to room temperature, then is placed in air atmosphere under the conditions of 250 DEG C, with
200 DEG C/h rise to 950 DEG C, and constant temperature calcining 4 hours obtains carrier；
2）Nickel nitrate 91g is weighed, is placed in the ammoniacal liquor that mass percentage concentration is 35% and is stirred untill without insoluble matter,
Obtain nickel element and co-impregnated solution of the concentration as 4.0g/100ml is counted using NiO.
With step 2）Gained co-impregnated solution 100ml is uniformly sprayed on step 1）Impregnated on resulting vehicle 100g, and constantly
Upset is shaken up, then the carrier after dipping is placed in into drying 4 hours at 125 DEG C, after temperature is down to room temperature, is risen with 200 DEG C/h
Temperature is to 550 DEG C, constant temperature calcining（Vacuum is 0.01MPa）2 hours, catalyst is obtained, numbering is catalyst B.
Catalyst B is by using mass ratio as 75：Carrier made from 2 calcite powder and adhesive A .S glue and it is carried on
NiO compositions on carrier, wherein, NiO weight/mass percentage composition is 4%.
Embodiment 3, the catalyst for preparing catalytically liquefying biomass oil
The step of according to embodiment 1, only by step 1）The temperature of drying is replaced by " being dried 4 hours under the conditions of 200 DEG C "
For " under the conditions of 300 DEG C dry 8 hours ", heating step is replaced with that " 300 DEG C/h rise by " 200 DEG C/h rise to 900 DEG C "
To 1000 DEG C ", the time of constant temperature calcining was replaced with 4 hours by 2 hours, obtained carrier；
By step 2）The consumption of middle nickel nitrate replaces with 55g, obtains nickel element and counts concentration being total to as 3.0g/100ml using NiO
Immersion liquid.
By step 3）Dry condition replace with 150 DEG C dry 6 hours, after temperature is down to room temperature, with 200 DEG C/it is small
When be warming up to 600 DEG C, constant temperature calcining（Vacuum is 0.01MPa）4 hours, catalyst is obtained, numbering is catalyst C.
Catalyst C is by using mass ratio as 75：Carrier and load made from 1 calcite powder and bonding agent polyvinyl alcohol
In the NiO compositions on carrier, wherein, NiO weight/mass percentage composition is 3%.
Embodiment 4, with the catalytic liquefaction catalyst of preparation produce bio-oil
Test the intermittent high-pressure stirred autoclave in 2L（Parr Instruments Co.Moline, PA）It is middle to carry out.
In the present embodiment, balance weighs 120g microalgae powders and is placed in reactor, adds 480ml water, and it is micro- to add consumption
The catalyst A of algae silty amount 10%, is passed through nitrogen and drives air and be stirred until homogeneous mixing.Entirely react by PID control instrument control system
Temperature, regulation rotating speed knob is to 200 revs/min, heating treats that temperature in the kettle rises to 230 DEG C, and temperature control maintains stop for 30 minutes
The time is stayed, stops heating and cooling down reactor.Question response kettle is cooled to room temperature, opens reactor, and the mixed liquor after cooling is quiet
Initial gross separation after layering is put, then is dehydrated and obtains thick bio-oil.Idiographic flow is shown in Fig. 1.
The analysis of bio-oil Elemental Composition is determined with vario MACRO CHNS elemental analysers.Calorific value calculation is used
Channiwala and Parikh（2002）The calorific value calculation formula of proposition：
HHV=0.3491 × C+1.1783 × H+0.1005 × S-0.1034 × O-0.0151 × N-0.0211 × A
Wherein, C, H, S, O, N, A represent C element, H element, S elements, O elements, N element and ash content in bio-oil respectively
In mass percent.
The definition of bio-oil yield and liquefied fraction：
Liquefied fraction=（1- solid residues quality/material quality）×100%；
Oil productivity=（Bio-oil quality/material quality）×100%.
Wherein, solid residues quality is remaining insoluble solid residual substance quality after stratification and suction filtration, is micro-
Ash content and catalyst residue in algae raw material；Material quality is the raw material microalgae quality in addition reactor；Bio-oil quality
After layered suction filtration, viscous liquid that is water insoluble but being dissolved in organic solvent.
The component analysis of bio-oil is using Japanese Shimadzu Corporation（SHIMADZU）QP2010 gas chromatograph-mass spectrometers.
Product oil yield and quality is as shown in table 1 under the conditions of different catalysts
Product oil yield and quality under the conditions of table 1, different catalysts
（Note：The bio-oil that bio-oil A obtains for addition catalyst A；
The bio-oil that bio-oil B obtains for addition catalyst B；
The bio-oil that bio-oil C obtains for addition catalyst C；
Bio-oil D is not add bio-oil made from any catalyst）
As can be seen from Table 1, compared with not adding bio-oil made from any catalyst, it is made using the inventive method
Catalyst can be obviously improved the yield of bio-oil.Under conditions of catalyst made from the inventive method is present, obtain
Bio-oil compared with not adding bio-oil made from any catalyst, hydrogen content increase, phosphorus content reduction, nitrogen content drop
It is low.
Claims (12)
1. a kind of carbon monoxide-olefin polymeric, is made up of carrier and the metal oxide being carried on the carrier；
Wherein, the material for constituting carrier is clay mineral powder；
The clay mineral powder is calcite powder；
The metal oxide is NiO；
In the carbon monoxide-olefin polymeric, the mass percentage content of metal oxide is 2%-4%.
2. composition according to claim 1, it is characterised in that：In the carrier, the mesh number of clay mineral powder is 200
The mesh of mesh -300.
3. a kind of method for preparing carbon monoxide-olefin polymeric described in claim 1 or 2, comprises the following steps：
1) drying, roasting, obtain the carrier after mixing the clay mineral powder and binding agent；
2) with the solution impregnation steps 1 of group VIII metallic element salt) resulting vehicle, then by the carrier drying after dipping and roasting
Burn, obtain the carbon monoxide-olefin polymeric；
The step 2) group VIII metallic element salt solution in, group VIII metallic element salt be nickel nitrate.
4. method according to claim 3, it is characterised in that：The step 1) in, binding agent is polyvinyl alcohol or A.S
Glue；The mass ratio of clay mineral powder and binding agent is 75：1-2；
In the baking step, temperature is 200 DEG C -300 DEG C；Time is 4-8 hours；
In the calcination stepses, the atmosphere of roasting is air atmosphere；Heating rate is 200 DEG C/h -300 DEG C/h；Final temperature
For 900 DEG C -1000 DEG C；The time of roasting is 2-4 hours；
The step 2) group VIII metallic element salt solution in, solvent is ammoniacal liquor；The group VIII metallic element is molten
Concentration in liquid is calculated as 2.0g/100mL-4.0g/100mL with the concentration of metal oxide；
The step 2) in drying steps, temperature is 100 DEG C -150 DEG C, and the time is -6 hours 2 hours；
In the calcination stepses, the atmosphere of roasting is vacuum atmosphere；Heating rate is 100 DEG C/h -200 DEG C/h；Final temperature
For 500 DEG C -600 DEG C；The time of roasting is 1-4 hours.
5. method according to claim 4, it is characterised in that：The step 2) group VIII metallic element salt solution
In, the solvent is the ammoniacal liquor that mass percentage concentration is 35%；
In the calcination stepses, the vacuum of the vacuum atmosphere is 0.01MPa-0.02MPa.
6. application of the carbon monoxide-olefin polymeric described in claim 1 or 2 in bio-oil quality is improved：
The raising bio-oil quality is selected from following at least one：
1) yield of bio-oil is improved；
2) hydrogen content in bio-oil is improved；
3) phosphorus content in reduction bio-oil；
4) nitrogen content in reduction bio-oil.
7. application of the carbon monoxide-olefin polymeric described in claim 1 or 2 in bio-oil is prepared.
8. a kind of method for preparing bio-oil, comprises the following steps：Exist in carbon monoxide-olefin polymeric described in claim 1 or 2
Under conditions of, raw material microalgae powder and deionized water are mixed into row hydrothermal liquefaction, the bio-oil is obtained.
9. method according to claim 8, it is characterised in that：The consumption of the carbon monoxide-olefin polymeric is microalgae powder quality
5%-20%；
The mass ratio of the microalgae powder and water is 1：3-4.
10. method according to claim 9, it is characterised in that：The consumption of the carbon monoxide-olefin polymeric is microalgae powder quality
10%.
11. the method according to any one of claim 8-10, it is characterised in that：In the hydrothermal liquefaction step, temperature
For 200 DEG C -300 DEG C；
Time is -120 minutes 30 minutes.
12. method according to claim 11, it is characterised in that：In the hydrothermal liquefaction step, the temperature is 230
℃；
The time is 30 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105536849B (en) * | 2015-12-23 | 2018-04-03 | 清华大学 | A kind of mesoporous catalyst with hydrothermal stability, preparation method and the method for preparing bio oil with its catalysis hydrothermal liquefaction microalgae |
| CN105772076B (en) * | 2016-02-29 | 2018-05-15 | 清华大学 | A kind of mesoporous catalyst with hydrothermal stability, its preparation method and the method for preparing bio oil with its catalysis hydrothermal liquefaction microalgae |
| CN108686667B (en) * | 2017-04-11 | 2021-03-16 | 中国人民大学 | Catalyst for microalgae thermal liquefaction denitrification and preparation method and application thereof |
| RU2668423C1 (en) * | 2017-12-28 | 2018-10-01 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Catalyst for hydrothermal liquefaction of plant biomass |
| CN109294631B (en) * | 2018-09-14 | 2020-04-10 | 厦门大学 | Method for preparing bio-oil by catalytic liquefaction of microalgae |
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