Alcohol ether fuel based on graded catalytic conversion of biomass and preparation method of alcohol ether fuel

Abstract

The invention discloses an alcohol ether fuel based on biomass staged catalytic conversion and a preparation method thereof. The alcohol ether fuel based on biomass staged catalytic conversion comprises the following components in parts by weight: 50-80 parts of biomass alcohol ether base liquid; 0.5-5 parts of a rare earth composite catalytic synergist; 2-10 parts of a combustion-supporting stabilizer; 1-5 parts of an anti-explosion and anti-seismic agent; 0.5-3 parts of a cleaning dispersant; and 2-4 parts of a conditioning agent. The invention discloses a preparation method of alcohol ether fuel based on biomass graded catalytic conversion. The preparation method comprises the following steps: gasifying and purifying biomass to obtain synthesis gas; synthesizing a crude alcohol ether mixture under pressurization and catalysis conditions; rectifying, separating and blending to obtain a biomass alcohol ether base solution; preparing a rare earth composite catalytic synergist; the alcohol ether fuel is obtained by uniformly mixing all the components. The method has relatively high practicability, environmental protection property and economical efficiency, and is suitable for large-scale popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to an alcohol ether fuel and a preparation method thereof, and in particular to an alcohol ether fuel based on hierarchical catalytic conversion of biomass and a preparation method thereof. BACKGROUND

[0002] With the increasingly serious global energy crisis and environmental pollution problems, the development and utilization of renewable and clean biomass energy has become an important direction of energy transformation. Biomass energy is considered as one of the most potential alternative energy sources due to its wide source, renewable and carbon neutral characteristics. At present, the utilization methods of biomass energy mainly include direct combustion, gasification, liquefaction, fermentation to produce ethanol, etc., but these methods generally have problems such as low energy conversion efficiency, complex product composition, high subsequent processing cost, unstable combustion performance, etc.

[0003] In the field of industrial gas, although traditional fuels such as acetylene, propane and liquefied petroleum gas are widely used, they have problems such as high pollution during combustion, high safety hazards and dependence on fossil resources. Although some gas efficiency enhancers (such as the light alkane fuel gas rare earth catalytic efficiency enhancer disclosed in application number CN201310085431.8) can improve the combustion performance of gas, they are still limited to the modification of existing fossil gas and cannot fundamentally realize the green substitution of energy.

[0004] On the other hand, alcohol ether fuels (such as methanol, ethanol, dimethyl ether, etc.) are considered as ideal alternative fuels due to their high oxygen content, clean combustion and renewable advantages. However, pure alcohol ether fuels have problems such as low calorific value, slow combustion speed, strong corrosion and difficult low-temperature starting, which limit their large-scale industrial application.

[0005] Therefore, how to combine the efficient conversion of biomass resources with the performance optimization of alcohol ether fuels to develop a biomass-based alcohol ether fuel with high calorific value, high combustion efficiency, low pollution and high safety has become a technical problem to be solved in the current energy chemical industry. SUMMARY

[0006] In order to solve the above technical problems, the technical scheme adopted by the present application is as follows: an alcohol ether fuel based on hierarchical catalytic conversion of biomass, comprising the following components by weight:

[0007] In order to solve the above technical problems, the technical scheme adopted by the present application is as follows: an alcohol ether fuel based on hierarchical catalytic conversion of biomass, comprising the following components by weight: Biomass alcohol ether base liquid 50-80 parts; Rare earth composite catalytic efficiency enhancer 0.5-5 parts; Combustion stabilizer 2-10 parts; Anti-knock and anti-vibration agent 1-5 parts; Clean dispersing agent 0.5-3 parts; and, the regulator 2-4 parts. Further, the biomass alcohol ether base fluid includes the following components by weight: Methanol 20-40 parts; Ethanol 10-30 parts; Dimethyl ether 15-35 parts; C3-C5 higher alcohol 5-15 parts; Ester compound 3-10 parts; Water 2-10 parts.

[0008] Further, the rare earth composite catalytic synergist includes the following components by weight: Cerium nitrate 3-8 parts; Lanthanum nitrate 1-3 parts; Ferrocene 0.5-2 parts; Nano zinc oxide 1-4 parts; Ethanol 30-60 parts; Acetone 10-25 parts; Petroleum ether 10-20 parts; Surfactant 0.5-2 parts.

[0009] Further, the combustion-supporting stabilizer is selected from one or more of tert-butyl alcohol, methyl tert-butyl ether, isooctyl nitrate, and the total amount of addition is 2-10 parts.

[0010] Further, the anti-knock and anti-shock agent is selected from one or more of cyclopentadiene manganese tricarbonyl, methylcyclopentadiene manganese tricarbonyl, and tetraethyl lead substitutes.

[0011] Further, the cleaning dispersant is selected from one or more of polyisobutylene amine, polyether amine, and succinimide.

[0012] Further, the regulator is one or more of deionized water, methanol or ethanol, used to adjust the water content and viscosity of the fuel.

[0013] A preparation method of alcohol ether fuel based on biomass staged catalytic conversion, comprising the following steps: Step one, gasify the biomass raw material at 600-900℃, and obtain synthesis gas after purification; Step two, under the conditions of 2.0-6.0 MPa and 200-300℃, the synthesis gas is catalytically reacted by Cu-Zn-Al-La catalyst to obtain a crude alcohol ether mixture; Step three, the crude alcohol ether mixture is subjected to rectification to separate methanol, ethanol, dimethyl ether, C3-C5 higher alcohol and ester components, which are mixed in proportion and water is added to obtain a biomass alcohol ether base fluid; Step 4: After dissolving acetone and ferrocene, add ethanol, petroleum ether, and surfactant in sequence, stir evenly, then add cerium nitrate, lanthanum nitrate, and nano zinc oxide. After complete dissolution, filter to obtain rare earth composite catalytic synergist. Step 5: Under stirring conditions, rare earth composite catalyst enhancer, combustion stabilizer, anti-knock and anti-shock agent, cleaning dispersant and regulator are added sequentially to the biomass alcohol ether base liquid and mixed evenly to obtain alcohol ether fuel.

[0014] Furthermore, in step two, the molar ratio of each metal element in the Cu-Zn-Al-La catalyst is Cu:Zn:Al:La = (5~7):(2~3):1:(0.05~0.15).

[0015] Furthermore, the distillation in step three is carried out in a distillation column, with operating conditions of a top temperature of 60–75°C, a bottom temperature of 85–120°C, and a pressure of atmospheric pressure to 0.3 MPa.

[0016] This invention discloses an alcohol ether fuel based on biomass staged catalytic conversion and its preparation method. The alcohol ether fuel based on biomass staged catalytic conversion provided by this invention has the following outstanding advantages: the raw material is green and renewable, realizing the high-value utilization of biomass resources; it has excellent combustion performance, with high flame temperature, fast cutting speed, and short preheating time, and can completely replace acetylene and propane for industrial cutting; it has outstanding environmental characteristics, with extremely low sulfur and phosphorus content, no black smoke during combustion, and significantly reduced CO and HC emissions; it is safe to use, with a moderate flash point, narrow explosion limit range, and safe storage and transportation; it is multifunctional and applicable, and can be used as industrial fuel or as a clean fuel additive for vehicles, improving anti-knock properties and environmental friendliness; the process is mature and easy to industrialize, with strong raw material adaptability and good equipment versatility. Detailed Implementation

[0017] The technical solution adopted in this invention is: an alcohol-ether fuel based on biomass staged catalytic conversion, comprising the following components by weight: 50-80 parts of biomass alcohol ether-based liquid; 0.5–5 parts of rare earth composite catalytic synergist; Combustion stabilizer 2-10 parts; 1-5 parts of blast-resistant and shock-absorbing agent; Cleaning dispersant 0.5–3 parts; And, 2 to 4 parts of regulator. Furthermore, the biomass alcohol ether-based liquid comprises the following components in parts by weight: 20-40 parts of methanol; 10-30 parts ethanol; 15-35 parts of dimethyl ether; 5-15 parts of C3-C5 higher alcohols; 3 to 10 parts of ester compounds; 2 to 10 parts water.

[0018] The rare earth composite catalytic synergist comprises the following components in parts by weight: 3-8 parts of cerium nitrate; Lanthanum nitrate 1-3 parts; 0.5 to 2 parts of ferrocene; 1-4 parts of nano zinc oxide; 30-60 parts ethanol; 10-25 parts acetone; 10-20 parts of petroleum ether; Surfactant 0.5 to 2 parts.

[0019] The combustion stabilizer is selected from one or more of tert-butanol, methyl tert-butyl ether, and isooctyl nitrate, and the total amount added is 2 to 10 parts by weight.

[0020] The anti-blast and anti-vibration agent is selected from one or more of cyclopentadiene tricarbonyl manganese, methylcyclopentadiene tricarbonyl manganese, and tetraethyl lead substitutes.

[0021] The cleaning dispersant is selected from one or more of polyisobutyleneamine, polyetheramine, and succinimide.

[0022] The regulator is one or more of deionized water, methanol, or ethanol, used to adjust the water content and viscosity of the fuel.

[0023] The present invention will now be described in further detail with reference to specific embodiments.

[0024] Example 1:

[0025] (1) Preparation of biomass alcohol ether-based liquid

[0026] Dry and crushed corn stalks are used as raw materials and fed into a circulating fluidized bed gasifier. Under normal pressure and temperature conditions, steam and oxygen (steam / biomass mass ratio = 0.8, oxygen / biomass mass ratio = 0.3) are introduced to carry out the gasification reaction.

[0027] The generated gas is purified by cyclone dust removal, water washing, desulfurization (using iron oxide desulfurizer) and decarbonization (using pressure swing adsorption) to obtain syngas (volume composition: H2 45%, CO 30%, CO2 20%, CH4 5%).

[0028] Syngas is introduced into a fixed-bed reactor packed with a CuZnAlLa catalyst, the molar composition of which is Cu:Zn:Al:La = 5:2.5:1:0.05.

[0029] The reaction products were condensed to obtain a crude alcohol-ether mixture.

[0030] The crude alcohol-ether mixture was fed into a distillation column, and the top temperature was controlled at 68°C, the bottom temperature at 105°C, and the pressure at 0.1 MPa for separation. The fractions were collected to obtain the following components (by weight): 32 parts of methanol 18 parts of ethanol 22 parts of dimethyl ether 5 parts of C3-C5 higher alcohols such as propanol and butanol 6 parts of esters such as methyl acetate and ethyl acetate 6 parts water Mix the above components evenly to obtain a biomass alcohol ether-based liquid.

[0031] (2) Preparation of rare earth composite catalytic synergists

[0032] In a clean preparation container, add 15 parts acetone and 2 parts ferrocene, and stir slowly with a glass rod until the ferrocene is completely dissolved.

[0033] Add 60 parts of ethanol, 15 parts of petroleum ether, and 0.5 parts of polyoxyethylene ether (surfactant) in sequence, and continue stirring for 15 minutes.

[0034] Add 5 parts cerium nitrate, 2 parts lanthanum nitrate, and 1 part nano zinc oxide, and stir until completely dissolved.

[0035] The mixture was filtered through a 500-mesh filter to obtain a clear and transparent rare earth composite catalytic enhancer.

[0036] (3) Blending of alcohol-ether fuels

[0037] Take 70 parts of the above biomass alcohol ether base liquid and place it in a mixing vessel, then turn on the stirring.

[0038] Add the following ingredients in sequence: 3 parts rare earth composite catalytic enhancer, 5 parts methyl tert-butyl ether (combustion stabilizer), 3 parts methylcyclopentadiene manganese tricarbonyl (anti-explosion and anti-shock agent), 2 parts polyisobutylene amine (cleaning dispersant), and 3 parts deionized water (regulator).

[0039] Stir for 40 minutes to ensure that all components are fully mixed and homogeneous, thus obtaining the biomass alcohol ether fuel of the present invention (denoted as fuel A).

[0040] Example 2:

[0041] (1) Preparation of biomass alcohol ether-based liquid

[0042] Wood chips were used as raw material and fluidized bed gasification was carried out at 800℃, with a water vapor / biomass mass ratio of 0.7 and an oxygen / biomass mass ratio of 0.25.

[0043] The composition of the purified syngas is approximately: H2 42%, CO 28%, CO2 22%, CH4 8%.

[0044] Catalytic synthesis conditions: pressure 5.0 MPa, temperature 260℃, catalyst Cu:Zn:Al:La = 7:2.8:1:0.08, space velocity 2800 h⁻¹.

[0045] Distillation conditions: top temperature 70℃, bottom temperature 110℃, pressure 0.15 MPa.

[0046] Collect and mix to obtain the base liquid components (parts by weight): 20 parts methanol 30 parts of ethanol 28 parts of dimethyl ether 10 parts of C3~C5 higher alcohols 3 parts of ester compounds 2 parts water

[0047] (2) Preparation of rare earth composite catalytic synergists

[0048] Take 25 parts of acetone and dissolve 1.2 parts of ferrocene.

[0049] Add 30 parts of ethanol, 18 parts of petroleum ether, and 1.5 parts of alkylphenol polyoxyethylene ether, and stir for 12 minutes.

[0050] Add 6 parts cerium nitrate, 1.8 parts lanthanum nitrate, and 4 parts nano zinc oxide, dissolve, and then filter through a 450-mesh filter.

[0051] (3) Blending of alcohol-ether fuels

[0052] Take 65 parts of biomass alcohol ether base liquid.

[0053] Add the following: 4 parts of the above-mentioned synergist, 8 parts of tert-butanol (combustion stabilizer), 2 parts of cyclopentadiene manganese tricarbonyl (anti-explosion and anti-shock agent), 1.5 parts of polyetheramine (cleaning and dispersing agent), and 2.5 parts of methanol (regulator).

[0054] Stir for 35 minutes to obtain fuel B. This formula focuses on high combustion rate and is suitable for continuous operation of thick plates where cutting efficiency is extremely important.

[0055] Example 3:

[0056] (1) Preparation of biomass alcohol ether-based liquid

[0057] Using rice husks as raw material, the mixture is vaporized at 750℃, with a water vapor / biomass mass ratio of 0.9, and no additional oxygen is required (it is self-heating).

[0058] The composition of the purified syngas is approximately: H2 38%, CO 25%, CO2 30%, CH4 7%.

[0059] Catalytic synthesis conditions: pressure 3.0 MPa, temperature 220℃, catalyst Cu:Zn:Al:La = 5.5:3:1:0.12, space velocity 3500 h⁻¹.

[0060] Distillation conditions: Top temperature 63℃, bottom temperature 95℃, atmospheric pressure operation.

[0061] Collect and mix to obtain the base liquid components (parts by weight): 35 parts of methanol 10 parts of ethanol 15 parts dimethyl ether 15 parts of C3~C5 higher alcohols 8 parts of ester compounds 10 parts water

[0062] (2) Preparation of rare earth composite catalytic synergists

[0063] Take 12 parts of acetone and dissolve 0.5 parts of ferrocene.

[0064] Add 55 parts ethanol, 10 parts petroleum ether, and 0.8 parts fatty acid polyoxyethylene ester, and stir for 18 minutes.

[0065] Add 3 parts cerium nitrate, 1 part lanthanum nitrate, and 1.5 parts nano zinc oxide, dissolve, and then filter through a 400-mesh filter.

[0066] (3) Blending of alcohol-ether fuels

[0067] Take 75 parts of biomass alcohol ether base liquid.

[0068] Add the following: 1.5 parts of the above-mentioned synergist, 6 parts of a mixture of methyl tert-butyl ether and isooctyl nitrate (3:1) combustion improver, 1.5 parts of methylcyclopentadiene manganese tricarbonyl, 2.2 parts of succinimide (cleaning dispersant), and 3 parts of deionized water (regulator).

[0069] Stir for 45 minutes to obtain fuel C. This formula has a high base liquid ratio, requires less synergist, has a more cost-effectiveness, and also has a high flash point and good storage stability.

[0070] Example 4:

[0071] (1) Preparation of biomass alcohol ether-based liquid

[0072] The raw materials and gasification steps are the same as in Example 1, and the composition of the syngas is similar.

[0073] The catalytic synthesis conditions were adjusted to: pressure 2.5 MPa, temperature 210℃, and catalyst Cu:Zn:Al:La = 5.8:2:1:0.15, in order to improve the yield of oxygen-containing components.

[0074] Distillation conditions: top temperature 65℃, bottom temperature 100℃, pressure 0.05 MPa.

[0075] Collect and mix to obtain the base liquid components (parts by weight): 40 parts of methanol 25 parts of ethanol 35 parts dimethyl ether 6 parts of C3~C5 higher alcohols 4 parts of ester compounds 5 parts water

[0076] (2) Preparation of rare earth composite catalytic synergists

[0077] Take 10 parts of acetone and dissolve 1.5 parts of ferrocene.

[0078] Add 40 parts of ethanol, 20 parts of petroleum ether, and 1.8 parts of polyoxyethylene ether, and stir for 10 minutes.

[0079] Add 8 parts cerium nitrate, 3 parts lanthanum nitrate, and 3 parts nano zinc oxide, dissolve, and then filter through a 500-mesh filter.

[0080] (3) Blending of alcohol-ether fuels

[0081] Take 55 portions of biomass alcohol ether base liquid.

[0082] Add the following: 4.5 parts of the above-mentioned synergist, 9 parts of isooctyl nitrate (combustion stabilizer), 4 parts of tetraethyl lead substitute (explosion and shock resistant agent), 2.5 parts of a 1:1 mixture of polyisobutylene amine and polyether amine cleaning agent, and 3.5 parts of ethanol (modifier).

[0083] Stir for 50 minutes to obtain Fuel D. This formula focuses more on improving anti-knock properties and reducing emissions, optimizing its overall performance as a gasoline additive.

[0084] The following performance comparison table records the performance test results of fuel A in metal cutting; Fuel A was filled into a standard industrial gas cylinder and used to cut 30mm thick Q235 carbon steel plates. The results were compared with commercially available propane cutting gas and acetylene gas, as shown in the table below: Performance Comparison Table of Test Items

[0085] The following records the physicochemical properties and environmental performance tests of fuel A; Test Items and Test Results Table

[0086] Table of Fuel A Blending Test Results

[0087] The following records a performance comparison of fuels with different formulations; three fuels were prepared and compared by adjusting the ratio of biomass alcohol ether-based liquid to catalytic enhancer: Fuel composition and performance parameter table

[0088] The rare earth composite catalytic synergist of this invention and the synergist (cerium nitrate + ferrocene system) disclosed in CN103160348B were respectively added to the same batch of biomass alcohol ether-based liquid, and their combustion performance was compared: Comparison table of synergists

[0089] As can be seen from the above embodiments, the alcohol-ether fuel based on biomass staged catalytic conversion provided by the present invention has the following outstanding advantages: the raw material is green and renewable, realizing the high-value utilization of biomass resources; it has excellent combustion performance, with high flame temperature, fast cutting speed, and short preheating time, and can completely replace acetylene and propane for industrial cutting; it has outstanding environmental characteristics, with extremely low sulfur and phosphorus content, no black smoke during combustion, and significantly reduced CO and HC emissions; it is safe to use, with a moderate flash point, narrow explosion limit range, and safe storage and transportation; it is multifunctional and applicable, and can be used for industrial fuels as well as as a clean fuel additive for vehicles, improving anti-knock properties and environmental friendliness; the process is mature and easy to industrialize, with strong raw material adaptability and good equipment versatility.

[0090] The above embodiments are not intended to limit the present invention, and the present invention is not limited to the examples given above. Any changes, modifications, additions or substitutions made by those skilled in the art within the scope of the technical solution of the present invention are also within the protection scope of the present invention.

Claims

1. An alcohol-ether fuel based on biomass staged catalytic conversion, characterized in that, The components include the following parts by weight: 50-80 parts of biomass alcohol ether-based liquid; 0.5–5 parts of rare earth composite catalytic synergist; Combustion stabilizer 2-10 parts; 1-5 parts of blast-resistant and shock-absorbing agent; Cleaning dispersant 0.5–3 parts; And, 2 to 4 parts of regulator.

2. The alcohol-ether fuel based on biomass staged catalytic conversion according to claim 1, characterized in that: The biomass alcohol ether-based liquid comprises the following components in parts by weight: 20-40 parts of methanol; 10-30 parts ethanol; 15-35 parts of dimethyl ether; 5-15 parts of C3-C5 higher alcohols; 3 to 10 parts of ester compounds; 2 to 10 parts water.

3. The alcohol-ether fuel based on biomass staged catalytic conversion according to claim 1, characterized in that: The rare earth composite catalytic synergist comprises the following components in parts by weight: 3-8 parts of cerium nitrate; Lanthanum nitrate 1-3 parts; 0.5 to 2 parts of ferrocene; 1-4 parts of nano zinc oxide; 30-60 parts ethanol; 10-25 parts acetone; 10-20 parts of petroleum ether; Surfactant 0.5 to 2 parts.

4. The alcohol-ether fuel based on biomass staged catalytic conversion according to claim 1, characterized in that: The combustion stabilizer is selected from one or more of tert-butanol, methyl tert-butyl ether, and isooctyl nitrate, and its total addition amount is 2 to 10 parts.

5. The alcohol-ether fuel based on biomass staged catalytic conversion according to claim 1, characterized in that: The anti-explosion and anti-vibration agent is selected from one or more of cyclopentadiene manganese tricarbonyl, methylcyclopentadiene manganese tricarbonyl, and tetraethyl lead substitutes.

6. The alcohol-ether fuel based on biomass staged catalytic conversion according to claim 1, characterized in that: The cleaning dispersant is selected from one or more of polyisobutyleneamine, polyetheramine, and succinimide.

7. The alcohol-ether fuel based on biomass staged catalytic conversion according to claim 1, characterized in that: The regulator is one or more of deionized water, methanol, or ethanol, used to adjust the water content and viscosity of the fuel.

8. A method for preparing alcohol-ether fuel based on biomass staged catalytic conversion according to any one of claims 1-7, characterized in that, Includes the following steps: Step 1: The biomass raw material is gasified at 600-900℃ and purified to obtain syngas; Step 2: The synthesis gas is subjected to a Cu-Zn-Al-La catalyst under conditions of 2.0–6.0 MPa and 200–300 °C to obtain a crude alcohol-ether mixture. Step 3: The crude alcohol-ether mixture is distilled to separate methanol, ethanol, dimethyl ether, C3-C5 higher alcohols and ester components, which are then mixed in proportion and adjusted with water to obtain a biomass alcohol-ether base liquid. Step 4: After dissolving acetone and ferrocene, add ethanol, petroleum ether, and surfactant in sequence, stir evenly, then add cerium nitrate, lanthanum nitrate, and nano zinc oxide. After complete dissolution, filter to obtain rare earth composite catalytic synergist. Step 5: Under stirring conditions, the rare earth composite catalytic enhancer, combustion stabilizer, anti-knock and anti-shock agent, cleaning dispersant and regulator are added sequentially to the biomass alcohol ether base liquid and mixed evenly to obtain the alcohol ether fuel.

9. The method for preparing alcohol-ether fuels based on biomass staged catalytic conversion according to claim 8, characterized in that: The molar ratio of each metal element in the Cu-Zn-Al-La catalyst in step two is Cu:Zn:Al:La = (5-7):(2-3):1:(0.05-0.15).

10. The method for preparing alcohol-ether fuel based on biomass staged catalytic conversion according to claim 8, characterized in that: The distillation in step three is carried out in a distillation column, with operating conditions of a top temperature of 60-75°C, a bottom temperature of 85-120°C, and a pressure of atmospheric pressure to 0.3 MPa.

Images