CN107029730B - Titanium dioxide loaded thulium-nickel catalyst and preparation method and application thereof - Google Patents
Titanium dioxide loaded thulium-nickel catalyst and preparation method and application thereof Download PDFInfo
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- CN107029730B CN107029730B CN201610080084.3A CN201610080084A CN107029730B CN 107029730 B CN107029730 B CN 107029730B CN 201610080084 A CN201610080084 A CN 201610080084A CN 107029730 B CN107029730 B CN 107029730B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/008—Controlling or regulating of liquefaction processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention discloses a titanium dioxide loaded thulium-nickel catalyst, and a preparation method and application thereof. The preparation method of the titanium dioxide loaded thulium-nickel catalyst comprises the following steps: 1) acidifying titanium dioxide powder; 2) mixing the solution treated in the step 1) with a nickel salt solution, and oscillating; 3) mixing the mixed solution treated in the step 2) with a thulium salt solution, oscillating, standing, taking solid precipitate in the system after standing, drying and roasting to obtain the titanium dioxide loaded thulium-nickel catalyst. The titanium dioxide loaded thulium-nickel catalyst can be used for carrying out catalytic liquefaction on the direct excrement liquefaction process, and can improve the yield of biomass oil produced by the direct excrement liquefaction reaction at a lower temperature.
Description
Technical Field
The invention relates to a titanium dioxide loaded thulium-nickel catalyst, a preparation method and application thereof, and belongs to the technical field of chemical catalysis and environmental energy engineering.
Background
With the acceleration of the urbanization process, the yield of urban excrement is continuously increased, and the urban excrement which is not effectively treated has risks of environment and health, so that attention and research are needed to a method for quickly, efficiently, harmlessly, resourcefully, stably and quantitatively treating the urban excrement.
The traditional treatment method of urban excrement often has the problems of incomplete treatment, low conversion efficiency, high energy consumption and water consumption and the like, and excrement is taken as a staggered resource, so that if the recovery of energy and resources can be realized by an effective treatment method, the method can serve multiple purposes. The direct liquefaction treatment method of the excrement is used as a novel treatment technology, the excrement is converted into the biomass oil, and harmlessness, reduction and recycling of the excrement are efficiently realized.
However, research on direct liquefaction of feces is still in the early stage, and the direct liquefaction process of feces needs to be carried out at high temperature and high pressure, which requires a great deal of energy consumption in the early stage.
Disclosure of Invention
The invention aims to provide a titanium dioxide loaded thulium-nickel catalyst, and a preparation method and application thereof. The titanium dioxide loaded thulium-nickel catalyst can be used for carrying out catalytic liquefaction on the direct excrement liquefaction process, and can improve the yield of biomass oil produced by the direct excrement liquefaction reaction at a lower temperature.
The preparation method of the titanium dioxide loaded thulium-nickel catalyst provided by the invention comprises the following steps: 1) acidifying titanium dioxide powder;
2) mixing the solution treated in the step 1) with a nickel salt solution, and oscillating;
3) mixing the mixed solution treated in the step 2) with a thulium salt solution, oscillating, standing, taking solid precipitate in the system after standing, drying and roasting to obtain the titanium dioxide loaded thulium-nickel catalyst.
In the preparation method, the acidified reagent is nitric acid solution;
the acidification time can be 12-48 h, and specifically can be 24 h.
In the above preparation method, the mass-to-volume ratio of the titanium dioxide powder to the acidifying agent may be 1g: (1.25-2) mL, specifically 1g:1.5 mL;
the mass percentage concentration of the acidified reagent can be 5-10%, specifically 5%.
In the above preparation method, the mass-to-volume ratio of the titania powder to the nickel salt solution may be 1g: 1.25-2 mL, specifically 1g:1.5 mL;
the molar concentration of the nickel salt solution can be 0.5-1.0 mol/L, and specifically can be 0.75 mol/L; the nickel salt solution is a nickel chloride solution, a nickel nitrate solution or a nickel sulfate solution;
in the step 2), the oscillation time can be 12-48 h, specifically 24h, 12-24 h or 24-48 h.
In the above preparation method, the mass-to-volume ratio of the titanium dioxide powder to the thulium salt solution may be 1g: 1.25-2 mL, specifically 1g:1.5 mL;
the molar concentration of the thulium salt solution can be 0.5-1.5 mol/L, specifically 1mol/L, 0.5-1 mol/L or 1-1.5 mol/L; the thulium salt solution is a thulium nitrate solution, a thulium sulfate solution or a thulium chloride solution;
in the step 3), the oscillation time can be 12-48 h, specifically 24 h; the standing time can be 8-16 h, specifically 12h or 12-16 h;
the drying temperature can be 102-108 ℃, particularly 105 ℃, and the drying time can be 8-12 hours, particularly 8 hours or 8-10 hours;
the roasting temperature can be 600-900 ℃, specifically 800 ℃, 600-800 ℃ or 800-900 ℃, and the roasting time can be 4-8 hours, specifically 4 hours or 4-6 hours.
The invention also provides the titanium dioxide loaded thulium-nickel catalyst prepared by the preparation method.
The titanium dioxide loaded thulium-nickel catalyst is applied to excrement liquefaction catalysis and/or in preparation of biomass oil.
The invention further provides a preparation method of the biomass oil, which comprises the following steps: mixing the titanium dioxide loaded thulium-nickel catalyst with fresh excrement, and directly carrying out liquefaction reaction to obtain the biomass oil.
In the preparation method, the mass ratio of the titanium dioxide loaded thulium-nickel catalyst to the dry matter of the fresh excrement can be 1-3: 20, specifically 1: 10;
the reaction temperature can be 250-340 ℃, and specifically can be 250 ℃, 260 ℃, 310 ℃, 320 ℃ or 340 ℃; the reaction time can be 0-60 min, specifically 30min, 60min or 30-60 min;
the reaction is followed by a separation step; the separation is carried out by adopting an extraction method, the extracted solvents are an organic phase and a water phase, and the organic phase is dichloromethane, tetrachloromethane or acetone.
The invention further provides the biomass oil prepared by the preparation method.
The invention has the following advantages:
the titanium dioxide loaded thulium-nickel catalyst can be used for carrying out catalytic liquefaction on the direct liquefaction process of excrement, thereby relieving the technological method of the process. Under the condition of no catalyst, the biomass oil produced by direct liquefaction of the excrement has larger yield variation amplitude along with the variation of reaction temperature, and the highest yield (realized at 310 ℃) is 51.7 percent higher than the lowest yield (realized at 250 ℃); under the condition that the titanium dioxide loaded thulium-nickel catalyst exists, the biomass oil yield is smaller in variation amplitude along with the reaction temperature, and the highest yield (realized at 320 ℃) is 18.8% higher than the lowest yield (realized at 260 ℃); therefore, the titanium dioxide loaded thulium-nickel catalyst can improve the yield of the biomass oil at a lower reaction temperature and save the energy of the reaction.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of titanium dioxide Supported Thulium Nickel catalyst
Adding 36g of titanium dioxide powder into 45mL of 5% nitric acid solution, mixing, acidifying and standing for 24 hours; then adding 45mL of 0.75mol/L nickel chloride solution (prepared by dissolving nickel chloride hexahydrate in water), mixing, and oscillating for 24h in a constant-temperature oscillator; then adding 45mL of 1mol/L thulium nitrate solution (prepared by dissolving thulium trioxide in nitric acid solution), and continuing mixing and oscillating for 24 h; standing for 12h, pouring out supernatant, and drying the residual solid in an oven at 105 ℃ for 8 h; and continuously putting the dried solid into a muffle furnace to be roasted for 4 hours at 800 ℃ to obtain the titanium dioxide loaded thulium-nickel catalyst.
Example 2 preparation of Biomass oil catalyzed by titanium dioxide loaded thulium-nickel catalyst
Weighing fresh excrement, adding a titanium dioxide loaded thulium-nickel catalyst (the mass of the catalyst is 10% of the mass of dry excrement), performing direct liquefaction reaction at the reaction temperature of 250 ℃ for 30min, separating the generated biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 45.1%.
Compared with comparative example 1, the biomass oil yield of the invention is improved by (45.1-34.1)% -11%.
Example 3 preparation of Biomass oil catalyzed by titanium dioxide loaded thulium-nickel catalyst
Weighing fresh excrement, adding a titanium dioxide loaded thulium-nickel catalyst (the mass of the catalyst is 10% of the mass of dry excrement), performing direct liquefaction reaction at the reaction temperature of 260 ℃ for 30min, separating the generated biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 41.8%.
Compared with the comparative example 2, the yield of the biomass oil is improved by (41.8-35.3)% -6.5%.
Example 4 preparation of Biomass oil catalyzed by titanium dioxide loaded thulium-nickel catalyst
Weighing fresh excrement, adding a titanium dioxide loaded thulium-nickel catalyst (the mass of the catalyst is 10% of the mass of dry excrement), performing direct liquefaction reaction at the reaction temperature of 310 ℃ for 30min, separating the generated biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 48.4%.
When the titanium dioxide loaded thulium nickel catalyst is used for preparing the biomass oil at the high temperature of 320 ℃, the yield is 41.8%, compared with the preparation under the low temperature condition in the examples 2-4, the fluctuation range of the yield is small, which shows that the catalyst is less influenced by the temperature, compared with the yield of 51.8% in the comparative example 3, the catalyst can improve the yield of the biomass oil prepared under the low temperature condition, so that the reaction temperature does not need to be increased by dozens of degrees to improve the yield (51.8-48.4)% > 1.4%, and the catalyst can improve the yield of the biomass oil under the low temperature and save reaction energy.
Example 5 preparation of Biomass oil catalyzed by titanium dioxide loaded thulium-nickel catalyst
Weighing fresh excrement, adding a titanium dioxide loaded thulium-nickel catalyst (the mass of the catalyst is 10% of the mass of dry excrement), performing direct liquefaction reaction at the reaction temperature of 320 ℃ for 60min, separating the generated biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 49.6%.
Compared with comparative example 4, the biomass oil yield of the invention is improved by (49.6-44.7)% -4.9%.
Example 6 preparation of Biomass oil catalyzed by titanium dioxide loaded thulium-nickel catalyst
Weighing fresh excrement, adding a titanium dioxide loaded thulium-nickel catalyst (the mass of the catalyst is 10% of the mass of dry excrement), performing direct liquefaction reaction at the reaction temperature of 340 ℃ for 30min, separating the generated biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 47.1%.
Compared with the comparative example 5, the yield of the biomass oil is improved by (47.1-39.6)% -7.5%.
After the yield of the biomass oil generated by the reaction is analyzed, the invention discovers that the yield change amplitude of the biomass oil generated by directly liquefying the excrement is larger along with the change of the reaction temperature under the condition of no catalyst, and the highest yield (realized at 310 ℃) is 51.7 percent higher than the lowest yield (realized at 250 ℃); in the presence of the titanium dioxide loaded thulium nickel catalyst, the biomass oil yield has small variation amplitude along with the reaction temperature, and the highest yield (realized at 320 ℃) is 18.8 percent higher than the lowest yield (realized at 260 ℃). The titanium dioxide loaded thulium-nickel catalyst can improve the yield of the biomass oil at a lower reaction temperature, and can improve the yield by 18.4-32.2%.
Comparative examples 1,
Directly liquefying fresh excrement in the absence of a catalyst, reacting at the reaction temperature of 250 ℃ for 30min, separating the produced biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 34.1%.
Comparative examples 2,
Directly liquefying fresh excrement in the absence of a catalyst, reacting at 260 ℃ for 30min, separating the produced biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction), weighing and analyzing, and obtaining the biomass oil with the yield of 35.3%.
Comparative examples 3,
Directly liquefying fresh excrement in the absence of a catalyst, reacting at the reaction temperature of 310 ℃ for 30min, separating the produced biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 51.8%.
Comparative examples 4,
Directly liquefying fresh excrement in the absence of a catalyst, reacting at the reaction temperature of 320 ℃ for 60min, separating the produced biomass oil by an extraction separation method (dichloromethane and water are adopted for extraction) after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 44.7%.
Comparative examples 5,
Directly liquefying fresh excrement in the absence of a catalyst, reacting at the reaction temperature of 340 ℃ for 30min, separating the produced biomass oil by an extraction separation (the extracting agent is dichloromethane) method after the reaction is finished, and weighing and analyzing to obtain the biomass oil with the yield of 39.6%.
Claims (7)
1. A preparation method of biomass oil comprises the following steps: mixing a titanium dioxide loaded thulium-nickel catalyst with fresh excrement, and directly carrying out liquefaction reaction to obtain the biomass oil;
the reaction temperature is 250-340 ℃; the reaction time is 30-60 min;
the titanium dioxide loaded thulium-nickel catalyst is prepared by the method comprising the following steps:
1) acidifying titanium dioxide powder;
2) mixing the solution treated in the step 1) with a nickel salt solution, and oscillating;
3) mixing the mixed solution treated in the step 2) with a thulium salt solution, oscillating, standing, taking solid precipitate in the system after standing, drying and roasting to obtain the titanium dioxide loaded thulium-nickel catalyst.
2. The method of claim 1, wherein: the acidizing reagent adopts a nitric acid solution;
the acidification time is 12-48 h.
3. The method of claim 2, wherein: the mass-to-volume ratio of the titanium dioxide powder to the acidified reagent is 1g: (1.25-2) mL;
the mass percentage concentration of the acidified reagent is 5-10%.
4. The production method according to any one of claims 1 to 3, characterized in that: the mass volume ratio of the titanium dioxide powder to the nickel salt solution is 1g: 1.25-2 mL;
the molar concentration of the nickel salt solution is 0.5-1.0 mol/L; the nickel salt solution is a nickel chloride solution, a nickel nitrate solution or a nickel sulfate solution;
in the step 2), the oscillation time is 12-48 h.
5. The production method according to any one of claims 1 to 3, characterized in that: the mass volume ratio of the titanium dioxide powder to the thulium salt solution is 1g: 1.25-2 mL;
the molar concentration of the thulium salt solution is 0.5-1.5 mol/L; the thulium salt solution is a thulium nitrate solution, a thulium sulfate solution or a thulium chloride solution;
in the step 3), the oscillation time is 12-48 h; the standing time is 8-16 h;
the drying temperature is 102-108 ℃, and the drying time is 8-12 h;
the roasting temperature is 600-900 ℃, and the roasting time is 4-8 h.
6. The method of claim 1, wherein: the mass ratio of the titanium dioxide loaded thulium-nickel catalyst to the dry matters of the fresh excrement is 1-3: 20;
the reaction is followed by a separation step; the separation is carried out by adopting an extraction method.
7. The biomass oil produced by the production method according to claim 1.
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| CN108671928B (en) * | 2018-05-04 | 2021-05-18 | 中国人民大学 | Catalyst for microalgae hydrothermal liquefaction and deoxidation and preparation method and application thereof |
| CN110449158A (en) * | 2018-05-08 | 2019-11-15 | 中国人民大学 | A kind of catalyst and the preparation method and application thereof for sludge hydrothermal liquefaction deoxidation |
| CN111983130A (en) * | 2020-09-07 | 2020-11-24 | 赵文建 | Method for detecting complete ammonia distillation based on full-automatic Kjeldahl determination instrument color method |
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