CN111548863A - Method for assisting biological oil catalytic cracking by superheated steam - Google Patents
Method for assisting biological oil catalytic cracking by superheated steam Download PDFInfo
- Publication number
- CN111548863A CN111548863A CN202010168557.1A CN202010168557A CN111548863A CN 111548863 A CN111548863 A CN 111548863A CN 202010168557 A CN202010168557 A CN 202010168557A CN 111548863 A CN111548863 A CN 111548863A
- Authority
- CN
- China
- Prior art keywords
- superheated steam
- oil
- catalytic cracking
- biological
- biological oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
Abstract
The invention discloses a superheated steam assisted biological oil catalytic cracking method, and belongs to the technical field of high-value utilization of biomass energy. Carrying out catalytic cracking on the biological grease under the assistance of superheated steam to prepare the biological fuel oil with higher olefin content; the temperature of the superheated steam is 500-600 ℃. The superheated steam is used in the catalytic cracking process, so that on one hand, a heat source is provided for the catalytic cracking of the biological oil, the superheated steam has good heat transfer performance, and the catalytic cracking conversion rate of the biological oil is improved; on the other hand, the superheated steam is pyrolyzed to generate proton hydrogen, so that the formation of olefin can be assisted, and the yield of olefin and alkane is improved.
Description
Technical Field
The invention belongs to the technical field of high-value utilization of biomass energy, and particularly relates to a superheated steam-assisted catalytic cracking method for biological oil.
Background
At present, the utilization of renewable energy is more and more researched, and the research of preparing the biofuel oil by taking the biological grease as the raw material is concerned by many researchers. There are several ways to utilize biological oils: first, the transesterification process produces first generation biodiesel, and the fatty acid esters formed by transesterification in the presence of acid and base catalysts can be combusted in an engine to provide heat. Secondly, the bio-fuel oil is prepared by catalytic cracking of the grease, and under the condition of an external heat source, the fatty acid can be effectively deoxidized by utilizing the catalytic action of an alkali metal or molecular sieve catalyst, so that a series of hydrocarbons are obtained, the molecular distribution of the molecular structure of the hydrocarbons distributed in petroleum components is very similar, and the hydrocarbons can also be used as a good fuel. In particular, after aromatization or isomerization, various fuels can be produced, including: bio-aviation kerosene, bio-gasoline, bio-diesel, and the like. Thirdly, the fatty acid raw material can be deoxidized to form a carbon chain distributed in C under the action of hydrogen and a hydrogenation catalyst15-C18The left and right alkanes can be directly used as diesel oil.
The catalytic cracking of biological grease is another important way for producing renewable liquid fuel, the catalytic cracking can effectively remove oxygen in carboxylic acid, most products of the base catalytic cracking mainly comprise about 75% of liquid fuel, 2% -5% of water, 15% -20% of gas products and 5% -10% of solid products, wherein the components of the liquid fuel mainly comprise olefin and alkane, the percentage is 70% -80%, and a small part of aromatic hydrocarbon and olefin. Many researchers use supported molecular sieve catalysts to perform catalytic cracking on biological grease, for example, CaO/ZSM-5 is used to crack biological grease, so that more aromatic compounds can be obtained than alkali catalytic cracking, and thus, the liquid fuel is more suitable for the application of biological aviation fuel. But the cracking conversion is not substantially changed, except that the aromatization of the ZSM-5 causes the structural change of the hydrocarbons. Also, MgO (ZnO)/SBA-15 and MgO (ZnO, Al) are used2O3) The catalyst such as MCM-41 is used for cracking, the yield of cracked liquid can be effectively improved orThe acid value of the product becomes high, etc. However, these molecular sieve-supported catalysts are relatively expensive to prepare, and if industrialization of biolipid is considered, the cost of the catalyst needs to be considered, and most of high-temperature catalytic cracking uses basic catalysts (CaO, Na)2CO3And the like), the components of the liquid fuel obtained by catalytic cracking are very similar to those of petroleum, wherein the high-olefin and alkane components endow the liquid components with good physical and chemical properties, and various physical and chemical properties including condensation point, acid value, thermogravimetric, density, viscosity and freezing point are very similar to those of commercial fuel oil. The molecular composition structure of the cracked oil component is regulated after aromatization or isomerization and partial hydrogenation, and the oil product can be prepared to meet the use standard of commercial fuel oil.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for assisting biological oil catalytic cracking by superheated steam, wherein efficient heat transfer is realized by using superheated steam for heat supply, the contents of alkane and olefin are increased under the action of superheated steam, and particularly the content of olefin is increased by nearly 10%.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a superheated steam assisted biological oil catalytic cracking method, under the assistance of superheated steam, carries on the catalytic cracking to the biological oil to prepare the biofuel with higher olefin content; the temperature of the superheated steam is 500-600 ℃.
The superheated steam assisted biological oil catalytic cracking method specifically comprises the following steps:
(1) adding a catalyst into a catalyst cage of a cracking reaction kettle, and starting stirring;
(2) the cracking reaction kettle is hermetically connected with the superheated steam generating device, a gas valve on the superheated steam generating device is opened to introduce superheated steam into the cracking reaction kettle, and the flow speed of the superheated steam is adjusted according to the set temperature in the cracking reaction kettle: when the temperature in the cracking reaction kettle is lower than a set temperature, the flow rate of the superheated steam is increased, and when the temperature in the cracking reaction kettle is higher than the set temperature, the flow rate of the superheated steam is reduced, and the temperature in the cracking reaction kettle is controlled to be the set temperature; the function of providing a heat source for the cracking reaction kettle by superheated steam is realized, and energy is saved;
(3) opening a feeding valve on the cracking reaction kettle, introducing biological grease into the kettle, and starting catalytic cracking reaction; when the main component of the condensed liquid is water, stopping introducing the superheated steam, and finishing the reaction.
In the method for assisting the catalytic cracking of the biological oil and fat by using the superheated steam, the set temperature in the cracking reaction kettle is 400-500 ℃.
In the method for assisting the catalytic cracking of the biological oil and fat by superheated steam, the catalyst is an alkali catalyst.
The superheated steam-assisted biological oil catalytic cracking method is characterized in that the catalyst is sodium carbonate.
In the method for assisting the catalytic cracking of the biological oil by the superheated steam, the dosage of the catalyst is 5-15% of the mass of the biological oil.
In the superheated steam assisted biological oil catalytic cracking method, the biological oil is any one of soybean oil, palm oil, acidified oil, illegal cooking oil or rubber seed oil.
According to the superheated steam assisted biological oil catalytic cracking method, the feeding rate of the biological oil is 5-6 g/s.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the superheated steam is used in the catalytic cracking process, on one hand, a heat source is provided for the catalytic cracking of the biological oil, the superheated steam has good heat transfer performance, and the energy consumption of the cracking reaction can be reduced by comparing with electric heating. Secondly, superheated steam can effectively contact with the raw materials, so that the catalytic cracking conversion rate of the biological oil is improved; on the other hand, the superheated steam is pyrolyzed to generate proton hydrogen, so that the formation of olefin can be assisted, and the yield of olefin and alkane is improved.
(2) The method carries out catalytic cracking on the waste biological oil under the assistance of superheated steam to prepare the carbon chain with the length of C6-C24The biological fuel oil of the components is subjected to superheated steam assisted catalytic cracking, so that the deoxygenation cracking capability of the grease is improved, the yield of olefin is improved, and the selectivity of olefin and alkane in the product is improved.
Drawings
FIG. 1 is a GC-MS diagram of the cracked products of examples 1 and 2, wherein FIG. 1-1 is a GC-MS diagram of the cracked product of example 1, and FIG. 1-2 is a GC-MS diagram of the cracked product of example 2;
FIG. 2 is a GC-MS diagram of the cleavage products of examples 3 and 4, wherein FIG. 2-1 is a GC-MS diagram of the cleavage product of example 3, and FIG. 2-2 is a GC-MS diagram of the cleavage product of example 4;
FIG. 3 is a GC-MS diagram of the cleavage products of examples 5 and 6, wherein FIG. 3-1 is a GC-MS diagram of the cleavage product of example 5, and FIG. 3-2 is a GC-MS diagram of the cleavage product of example 6.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
The method for catalytic cracking of sodium stearate comprises the following specific operation processes:
10g of sodium stearate is put into a superheater tube type furnace, and one end of the superheater tube type furnace is connected with a condensation receiving device. And (3) starting the reaction, heating the tubular furnace to 450 ℃ at the heating rate of 10 ℃/min until the reaction is finished when no condensed liquid flows out, condensing, standing and layering the liquid product, wherein the main component is liquid fuel oil. Finally, the liquid fuel product was subjected to GC-MS analysis, the results of which are shown in Table 1 and FIG. 1.
Example 2
The superheated steam assisted sodium stearate catalytic cracking method specifically comprises the following steps:
(1) putting 10g of sodium stearate into a superheater tube type furnace, wherein one end of the superheater tube type furnace is hermetically connected with a superheated steam generator, and the other end of the superheater tube type furnace is connected with a condensation receiving device;
(2) when the reaction starts, introducing 500 ℃ superheated steam into the superheater tube furnace, and controlling the flow rate of the superheated steam to ensure that the cracking reaction temperature is 450 ℃;
(3) when the collected condensed liquid is mainly water, stopping introducing the superheated steam, and finishing the reaction; condensing, standing and layering the liquid product, wherein the upper layer is liquid fuel oil, and the lower layer is distilled water; finally, the liquid product was taken for GC-MS analysis, and the results are shown in table 1 and fig. 1.
Example 3
The soybean oil catalytic cracking method comprises the following specific operation processes:
adding 100g of catalyst sodium carbonate into a catalyst cage of a cracking reaction kettle, and starting stirring; heating the cracking reaction kettle to 450 ℃ at the heating rate of 10 ℃/min; then 1000g of soybean oil is fed into the cracking reaction kettle through a nozzle, and the feeding rate is controlled at 5 g/s. Receiving liquid at the tail of the reactor until the reaction is finished when no condensed liquid is generated; after the reaction, the condensed liquid was subjected to GC-MS analysis, and the analysis results are shown in Table 1 and FIG. 2.
Example 4
The method for assisting soybean oil catalytic cracking by superheated steam comprises the following steps:
(1) adding 100g of catalyst sodium carbonate into a catalyst cage of a cracking reaction kettle, and starting stirring;
(2) the cracking reaction kettle is hermetically connected with the superheated steam generating device, and the set temperature in the cracking reaction kettle is 450 ℃; opening a valve on a superheated steam generating device to introduce superheated steam of 600 ℃ into the cracking reaction kettle, wherein the flow rate of the superheated steam is determined by the temperature in the cracking reaction kettle, when the temperature in the cracking reaction kettle is lower than a set temperature, the flow rate of the superheated steam is increased, and when the temperature in the cracking reaction kettle is higher than the set temperature, the flow rate of the superheated steam is reduced, and the temperature in the cracking reaction kettle is controlled to be the set temperature;
(3) opening a feeding valve on the cracking reaction kettle, introducing 1000g of soybean oil into the cracking reaction kettle, and starting catalytic cracking reaction; when the main component of the condensed liquid is water, stopping introducing the superheated steam, and finishing the reaction; the feeding rate of the soybean oil is controlled to be 5 g/s; the collected condensed liquid after the completion of the reaction was subjected to GC-MS analysis, and the results are shown in Table 1 and FIG. 2.
Example 5
The method for catalytic cracking of the acidified oil comprises the following specific operation processes:
adding 100g of catalyst sodium carbonate into a catalyst cage of a cracking reaction kettle, and starting stirring; heating the cracking reaction kettle to 450 ℃ at the heating rate of 10 ℃/min, and simultaneously introducing 1000g of acidified oil into the cracking reaction kettle from a nozzle, wherein the feeding rate is controlled at 5 g/s. Receiving liquid at the tail of the reactor until the reaction is finished when no condensed liquid is generated; after the reaction, the condensed liquid was subjected to GC-MS analysis, and the analysis results are shown in Table 1 and FIG. 2.
Example 6
The superheated steam assisted method for catalytic cracking of acidified oil specifically comprises the following steps:
(1) adding 100g of catalyst sodium carbonate into a catalyst cage of a cracking reaction kettle, and starting stirring;
(2) the cracking reaction kettle is hermetically connected with the superheated steam generating device, and the temperature in the cracking reaction kettle is set to be 450 ℃; opening a valve on a superheated steam generating device to introduce superheated steam of 600 ℃ into the cracking reaction kettle, wherein the flow rate of the superheated steam is determined by the temperature in the cracking reaction kettle, when the temperature in the cracking reaction kettle is lower than a set temperature, the flow rate of the superheated steam is increased, and when the temperature in the cracking reaction kettle is higher than the set temperature, the flow rate of the superheated steam is reduced, and the temperature in the cracking reaction kettle is controlled to be at the set temperature;
(3) opening a valve on the cracking reaction kettle, introducing 1000g of acidified oil into the kettle, and starting catalytic cracking reaction; when the main component of the condensed liquid is water, stopping introducing the superheated steam, and finishing the reaction; the feed rate of soybean oil was 5 g/s; the collected condensed liquid after the completion of the reaction was subjected to GC-MS analysis, and the results are shown in Table 1 and FIG. 3.
In summary of examples 1-6, it was found from the catalytic cracking results of the sodium stearate model compound in Table 1 that the yields of olefins and alkanes in the sodium stearate catalytic cracking products are 80% -90%, wherein the conversion rate of cracking is increased by about 5% and the content of olefins is increased by about 10% when superheated steam is introduced to assist the catalytic cracking, compared with the case where superheated steam is not introduced; FIG. 1 is a GC-MS test chart of the catalytic cracking products of examples 1 and 2, and it can be seen from FIG. 1 that the main components of the cracking products are olefins and paraffins, and the distribution of the paraffins and olefins with long carbon chains in the cracking products of example 2 is increased, which shows that after superheated steam is introduced, a part of the long carbon chains can be prevented from being re-cracked into short chain hydrocarbons.
In examples 3-6, the metal salt sodium carbonate is used as a catalyst to catalytically crack the bio-oil acidified oil and the soybean oil, and as can be seen from table 1 and fig. 2 and 3, as in the cracking case of the model compound, the cracking products are mainly alkanes and alkenes, but the cracking conversion rate is lower relative to the model compound, because the bio-oil has more or less impurities and water. In the cracking by introducing the superheated steam, the superheated steam is found to improve the cracking conversion rate by 5 percent or more, and simultaneously, the olefin content and the alkane content in the cracked product can be effectively improved, particularly, the olefin content is improved by about 10 percent. The contents of the olefin and the alkane are improved, one part is the cracking conversion rate, so that the contents of the olefin and the alkane are improved, the superheated water vapor provides proton hydrogen, the dehydration probability and effect of alcohol in the cracking process are increased, and the contents of the olefin and the alkane are improved.
Table 1 examples Change in component Selectivity during reaction
Claims (8)
1. A superheated steam-assisted biological oil catalytic cracking method is characterized in that biological oil is catalytically cracked under the assistance of superheated steam to prepare biofuel oil with high olefin content; the temperature of the superheated steam is 500-600 ℃.
2. A superheated steam-assisted biological oil and fat catalytic cracking method as claimed in claim 1, which is characterized by comprising the following steps:
(1) adding a catalyst into a catalyst cage of a cracking reaction kettle, and starting stirring;
(2) the cracking reaction kettle is hermetically connected with a superheated steam generating device, a gas valve on the superheated steam generating device is opened to introduce superheated steam into the cracking reaction kettle, and the flow rate of the superheated steam is adjusted according to the set temperature in the cracking reaction kettle;
(3) opening a feeding valve on the cracking reaction kettle, introducing biological grease into the kettle, and starting catalytic cracking reaction; when the main component of the condensed liquid is water, stopping introducing the superheated steam, and finishing the reaction.
3. A superheated steam-assisted biological oil catalytic cracking method as claimed in claim 1 or 2, wherein the set temperature in the cracking reaction kettle is 400-500 ℃.
4. A superheated steam-assisted catalytic cracking method of biological oil and fat according to claim 1 or 2, wherein the catalyst is an alkali catalyst.
5. A superheated steam-assisted catalytic cracking method of biological oil and fat according to claim 1 or 2, wherein the catalyst is sodium carbonate.
6. A superheated steam-assisted biological oil and fat catalytic cracking method as claimed in claim 1 or 2, wherein the amount of the catalyst is 5-15% of the mass of the biological oil and fat.
7. A superheated steam-assisted catalytic cracking method of biological oil and fat according to claim 1 or 2, wherein the biological oil and fat is any one of soybean oil, palm oil, acidified oil, illegal cooking oil or rubber seed oil.
8. A superheated steam-assisted catalytic cracking method for biological oil and fat according to claim 1 or 2, wherein the feeding rate of the biological oil and fat is 5-6 g/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010168557.1A CN111548863A (en) | 2020-03-11 | 2020-03-11 | Method for assisting biological oil catalytic cracking by superheated steam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010168557.1A CN111548863A (en) | 2020-03-11 | 2020-03-11 | Method for assisting biological oil catalytic cracking by superheated steam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111548863A true CN111548863A (en) | 2020-08-18 |
Family
ID=72001868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010168557.1A Pending CN111548863A (en) | 2020-03-11 | 2020-03-11 | Method for assisting biological oil catalytic cracking by superheated steam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111548863A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723783A (en) * | 2008-10-10 | 2010-06-09 | 中国石油化工股份有限公司 | Method for producing low carbon olefin by steam cracking on vegetable fat |
| CN105907480A (en) * | 2016-06-03 | 2016-08-31 | 深圳市创宇百川环境科技有限公司 | Method and an apparatus for refining biomass fuel oil by hydration catalysis means |
| CN110002934A (en) * | 2019-04-15 | 2019-07-12 | 广西大学 | A method of low-carbon alkene is prepared by oleic acid |
-
2020
- 2020-03-11 CN CN202010168557.1A patent/CN111548863A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723783A (en) * | 2008-10-10 | 2010-06-09 | 中国石油化工股份有限公司 | Method for producing low carbon olefin by steam cracking on vegetable fat |
| CN105907480A (en) * | 2016-06-03 | 2016-08-31 | 深圳市创宇百川环境科技有限公司 | Method and an apparatus for refining biomass fuel oil by hydration catalysis means |
| CN110002934A (en) * | 2019-04-15 | 2019-07-12 | 广西大学 | A method of low-carbon alkene is prepared by oleic acid |
Non-Patent Citations (2)
| Title |
|---|
| 佚名: "《化工辞典》", 30 September 1973, 燃料化学工业出版社 * |
| 徐俊明等: "大豆油催化裂解放大实验研究", 《林产化学与工业》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Integrated catalytic conversion of waste triglycerides to liquid hydrocarbons for aviation biofuels | |
| Qiu et al. | Research progress in the preparation of high-quality liquid fuels and chemicals by catalytic pyrolysis of biomass: A review | |
| Perego et al. | Biomass upgrading through acid–base catalysis | |
| Xu et al. | Thermochemical conversion of triglycerides for production of drop-in liquid fuels | |
| Maity | Opportunities, recent trends and challenges of integrated biorefinery: Part II | |
| Lestari et al. | Transforming triglycerides and fatty acids into biofuels | |
| Shun et al. | Recent progress of catalytic pyrolysis of biomass by HZSM-5 | |
| Ma et al. | A review of thermal–chemical conversion of lignocellulosic biomass in China | |
| US7816570B2 (en) | Process for conversion of biomass to fuel | |
| CA2663592C (en) | Method of converting triglycerides to biofuels | |
| Li et al. | Catalytic cracking of triglycerides with a base catalyst and modification of pyrolytic oils for production of aviation fuels | |
| EP2719746B1 (en) | Method for preparing fuel from biological oil and fat | |
| CN101831328B (en) | Green fuel oil and preparation method thereof | |
| WO2013086762A1 (en) | Fuel preparation method using biological grease | |
| Yin et al. | Review of bio-oil upgrading technologies and experimental study on emulsification of bio-oil and diesel | |
| Yan et al. | Catalytic conversion of triglycerides to liquid biofuels through transesterification, cracking, and hydrotreatment processes | |
| Zhao et al. | Production of biojet fuels from biomass | |
| Wang et al. | Microwave-assisted pyrolysis of vegetable oil soapstock: Comparative study of rapeseed, sunflower, corn, soybean, rice, and peanut oil soapstock | |
| WO2017222566A1 (en) | Macroscopic artificial dielectric susceptor for making biochemicals | |
| CN111548863A (en) | Method for assisting biological oil catalytic cracking by superheated steam | |
| Wang et al. | Pyrolysis of different types of waste cooking oil in the presence/absence HZSM-5 catalyst: Influence of feedstock characteristics on aromatic formation | |
| SIVRIU et al. | Theoretical and practical aspects for thermal treatment of waste vegetable oils | |
| Bagheri et al. | Biodiesel and green diesel production, upgrading of fats and oils from renewable sources | |
| Śmigiera et al. | Methanol as hydrogen donor in the alternative fuel synthesis | |
| Yadav et al. | Subcritical and Supercritical Water Treatments for Bio-Oil Production and Upgrading |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |