CN111054217A - Method for dehydrating and separating biological oil by using T-shaped zeolite membrane and regenerating membrane thereof - Google Patents
Method for dehydrating and separating biological oil by using T-shaped zeolite membrane and regenerating membrane thereof Download PDFInfo
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- CN111054217A CN111054217A CN201911296179.9A CN201911296179A CN111054217A CN 111054217 A CN111054217 A CN 111054217A CN 201911296179 A CN201911296179 A CN 201911296179A CN 111054217 A CN111054217 A CN 111054217A
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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Abstract
The invention discloses a method for dehydrating and separating biological oil by using a T-shaped zeolite membrane and a membrane regeneration method thereof. The method specifically comprises the following steps: (1) preparing a synthesis liquid precursor, and synthesizing the T-shaped zeolite membrane through hydrothermal crystallization; (2) sealing the synthesized T-shaped zeolite membrane, and dehydrating and separating the bio-oil by pervaporation; (3) the T-shaped zeolite membrane polluted by the biological oil in the separation process is regenerated to restore the separation performance, and is recycled for dehydration and separation of the biological oil. Compared with traditional separation methods such as distillation and the like, the novel process for the dehydration and separation of the biological oil by using the T-shaped zeolite membrane developed by the invention has the advantages of low energy consumption, simple operation, high selectivity and the like, and the green and efficient separation process has good application prospect in the development of the bio-based liquid fuel.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to a method for applying a T-shaped zeolite membrane to pervaporation dehydration separation of bio-oil and membrane regeneration of the bio-oil.
Background
The vigorous development of renewable bio-based energy is an important way to solve the problems of increasing shortage of fossil energy and related environmental pollution. Bio-oil is a complex liquid mixture obtained by rapid thermal cracking of biomass under high temperature conditions, and is considered as a potential renewable bio-based liquid fuel and has received extensive attention in both academia and industry. Because the directly obtained bio-oil generally has higher water content, the calorific value of the bio-oil is greatly reduced, and a plurality of adverse effects are brought to the refining processing of the bio-oil. Therefore, achieving efficient dehydration separation of bio-oil is of great importance to facilitate the development of new liquid fuels based on bio-oil.
The currently reported separation technology of bio-oil is mainly based on the traditional distillation method. Levens et al (patent publication No. CN 101693855A) reported a molecular distillation technique that successfully removed water and acid components from bio-oils by determining appropriate cold and hot face temperatures and distances. Rong Shuang et al (patent publication No. CN 102206141A) uses molecular distillation separation method to pre-treat bio-oil, and then obtains bio-oil fraction at 25-200 deg.C and 10-1800 Pa. However, higher distillation temperatures tend to cause bio-oil deterioration due to its heat sensitivity. On the other hand, the distillation process generally faces the problems of high energy consumption, low separation efficiency and the like, and the actual industrial production requirements are difficult to meet. The application of various commercialized organic nanofiltration and reverse osmosis membranes for bio-oil separation is reported by Teella (J.Membr.Sci.,2011,378,495-502) and the like, but the structure of the organic membrane materials is completely destroyed under a bio-oil system, and the organic membrane materials cannot be applied to a complex multi-component system of bio-oil. Legang et al (patent publication No. CN 109370666A) developed a graphene oxide membrane-based pervaporation membrane separation process for efficient dehydration of bio-oil, showing good separation selectivity and stability. Compared with the traditional distillation technology, the separation process can realize the separation of the bio-oil at normal temperature, not only can obviously reduce the separation energy consumption of the bio-oil, but also can prevent the bio-oil from deteriorating at high temperature. However, since the graphene oxide membrane has relatively poor mechanical properties, the membrane layer is easily damaged during use, which results in a decrease in separation performance. Therefore, it is of great significance to find membrane materials with good physical and chemical stability for dehydration and separation of bio-oil. The zeolite membrane has good physical and chemical stability and uniform microporous pore channel structure, so that the zeolite membrane is widely researched and used for dehydration and separation of various organic matter systems, but no report related to the dehydration and separation of biological oil is found at present.
Disclosure of Invention
The invention aims to develop a zeolite membrane material with good physical and chemical stability for the efficient dehydration of biological oil, and provides a T-shaped zeolite membrane for the dehydration separation of the biological oil and a membrane regeneration method thereof to solve the problem of membrane pollution of the zeolite membrane in a complex system of the biological oil.
The purpose of the invention is realized by the following technical scheme.
The T-type zeolite membrane is used for dehydration separation of biological oil and a membrane regeneration method thereof, and comprises the following steps:
(1) preparing a synthesis liquid precursor, and synthesizing the T-shaped zeolite membrane through hydrothermal crystallization;
(2) sealing the synthesized T-shaped zeolite membrane, and dehydrating and separating the bio-oil by adopting a pervaporation process;
(3) and (3) regenerating the T-shaped zeolite membrane polluted by the biological oil in the separation process of the step (2), and recycling the T-shaped zeolite membrane for dehydration and separation of the biological oil after the performance is recovered.
Further, SiO in the precursor of the synthetic liquid in the step (1)2:Al2O3:Na2O:K2O:H2The molar ratio of O is 1 (0.04-0.06), (0.20-0.30), (0.05-0.15) and (35-60); the temperature of the hydrothermal crystallization is 150-180 ℃; the hydrothermal crystallization time is 2-10 h.
Furthermore, the sealing mode in the step (2) is to seal one end of the T-shaped zeolite membrane by a polytetrafluoroethylene pipe sleeve, and the other end of the T-shaped zeolite membrane is connected with a vacuum pipeline.
Further, the feed side pressure in the pervaporation process in the step (2) is normal pressure, and the permeate side pressure is vacuum.
Further, the feeding temperature in the pervaporation process in the step (2) is 10-90 ℃.
Further, the bio-oil in the step (2) is prepared from lignocellulose through rapid thermal cracking; the water content of the bio-oil is 10-40 wt%, and the pH value is 1-3.
Further, the process conditions for the dehydration and separation of the bio-oil by the regenerated T-type zeolite membrane in the step (3) are the same as the process conditions in the step (2).
Further, the regeneration of the T-type zeolite membrane in the step (3) comprises the following steps: firstly, soaking the T-shaped zeolite membrane polluted by the bio-oil in ethanol/water solution at normal temperature for cleaning, then drying the cleaned T-shaped zeolite membrane, and then placing the dried T-shaped zeolite membrane in a muffle furnace for roasting to obtain the regenerated T-shaped zeolite membrane.
Furthermore, the concentration of ethanol in the ethanol/water solution is 40-90 wt%, the soaking time is 6-12 h, and the soaking times are 1-5.
Furthermore, the roasting temperature is 100-260 ℃, the roasting time is 6-12 h, and the heating and cooling rate is 0.5-1 ℃/min.
Compared with the prior art, the invention has the advantages that:
the separation process can realize the separation of the bio-oil at a lower temperature, obviously reduces the energy consumption for the separation of the bio-oil, has the characteristics of simplicity, high efficiency and good repeatability in the regeneration of the membrane, and can be circularly used for high-efficiency dehydration separation of a multi-component and strong-acid bio-oil system.
Drawings
FIG. 1 is a flow chart of the process of using T-type zeolite membrane in the separation of bio-oil by permeation, vaporization and dehydration.
1-heater, 2-stirrer, 3-T type zeolite membrane, 4-thermocouple, 5-pressure gauge, 6-cold trap, 7-valve, 8-buffer bottle and 9-vacuum pump.
Fig. 2 is an SEM picture of the T-type zeolite membrane used in the present invention after the membrane fouling occurred.
FIG. 3 is an SEM picture of a T-type zeolite membrane subjected to regeneration treatment in the invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
By using porous α -Al2O3The tube (the outer diameter is 13mm, the average pore diameter is 2-3 mu m) is used as a carrier tube, firstly, T-type zeolite molecular sieve seed crystals (the average particle diameter is 2 mu m) are deposited on the outer surface of the carrier tube through vacuum filtration, and the carrier tube is dried for standby. 1.6g of sodium hydroxide and 1.12g of potassium hydroxide were dissolved in 54g of deionized water, and then 0.82g of sodium aluminate was added to the above solution, followed by stirring at room temperature for 1 hour to obtain a clear solution. Then, 6g of a silica sol having a concentration of 40 wt% was slowly dropped into the above solution, and stirred for 12 hours to obtain a synthetic solution. Transferring the synthetic solution into a stainless steel reaction kettle, sealing two ends of the carrier tube pre-coated with the seed crystal, vertically placing the carrier tube in the reaction kettle, and carrying out hydrothermal crystallization at 150 ℃ for 4 hours after sealing. After the reaction was completed, the T-type zeolite membrane was repeatedly washed with deionized water to neutrality, and then dried at 80 ℃ overnight.
The bio-oil dehydration performance of the prepared T-type zeolite membrane was evaluated by the pervaporation process shown in fig. 1, in which the bio-oil (water content 40%, pH 1) was fed at 30 ℃, and the flux of the T-type zeolite membrane in the bio-oil system at 2 hours was 0.27kg · m-2·h-1The water content of the permeate side is greater than 98 wt%.
Example 2
Using the T-type zeolite membrane of example 1, the performance of the bio-oil separation by dehydration was evaluated by pervaporation. When the feed temperature of the bio-oil (water content is 40% and pH is 1) is 30 ℃, the flux of the T-type zeolite membrane in the bio-oil system for 36 hours is 0.13kg m-2·h-1The water content of the permeate side is greater than 98 wt%. The permeation flux of the membrane is significantly lower compared to example 1And the reduction shows that the T-type zeolite membrane generates membrane pollution in a bio-oil multi-component system. SEM pictures of the T-type zeolite membranes producing membrane fouling are shown in figure 2.
Example 3
Using the T-type zeolite membrane of example 1, the performance of the bio-oil separation by dehydration was evaluated by pervaporation. When the feed temperature of the bio-oil (water content is 40% and pH is 1) is 70 ℃, the flux of the T-type zeolite membrane in the bio-oil system for the 2 nd hour is 0.60kg m-2·h-1The water content of the permeate side is greater than 98 wt%.
Example 4
The contaminated zeolite membrane of example 2 was soaked in 90 wt% ethanol/water solution for 12h and the above washing process was repeated 3 times to remove bio-oil attached to the membrane surface. And drying the soaked T-shaped zeolite membrane, placing the dried T-shaped zeolite membrane in a muffle furnace, heating the T-shaped zeolite membrane from room temperature to 140 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 12 hours, and cooling the T-shaped zeolite membrane to the room temperature at the cooling rate of 1 ℃/min. The obtained T-shaped zeolite membrane is put into a solution of 50 wt% ethanol/water and soaked for 1 h. Finally drying in an oven at 60 ℃ for 3 h. The amount of contaminants on the zeolite membrane surface after regeneration is significantly reduced as shown in figure 3.
The bio-oil dehydration performance of the regenerated T-type zeolite membrane was evaluated by pervaporation, and when the feed temperature of the bio-oil (water content 40%, pH 1) was 70 ℃, the flux of the T-type zeolite membrane in the bio-oil system at 2h was 0.44kg m-2·h-1The water content of the permeate side is greater than 98 wt%.
Example 5
The calcination temperature of the zeolite membrane in example 4 was increased from 140 ℃ to 180 ℃ and the other conditions were kept constant.
The biological oil dehydration performance of the regenerated T-type zeolite membrane is evaluated by adopting a pervaporation process, and when the feeding temperature of the biological oil (the water content is 40 percent and the pH value is 1) is 70 ℃, the flux of the T-type zeolite membrane in the biological oil system for 2 hours is 0.46 kg.m-2·h-1The water content of the permeate side is greater than 98 wt%.
Example 6
The calcination temperature of the zeolite membrane in example 5 was increased from 180 ℃ to 220 ℃ and the other conditions were kept constant.
The bio-oil dehydration performance of the regenerated T-type zeolite membrane is evaluated by adopting a pervaporation process, and when the feed temperature of the bio-oil (the water content is 40 percent and the pH is 1) is 70 ℃, the flux of the T-type zeolite membrane in the bio-oil system for the 2 nd hour is 0.52 kg.m-2·h-1The water content of the permeate side is greater than 98 wt%.
Example 7
The zeolite membrane of example 6 was tested for stability of pervaporation performance under the same test conditions as in example 6. When the feed temperature of the bio-oil (water content is 40% and pH is 1) is 70 ℃, the flux of the T-type zeolite membrane in the bio-oil system for 5 hours is still 0.52 kg-m-2·h-1The water content of the permeate side is greater than 98 wt%. The permeation flux of the membrane remained unchanged compared to example 6, indicating that the regenerated type T zeolite membrane at 220 ℃ has better stability in the bio-oil multi-component system at 70 ℃.
Claims (10)
- The method for dehydrating and separating the biological oil and regenerating the T-shaped zeolite membrane is characterized by comprising the following steps of:(1) preparing a synthesis liquid precursor, and synthesizing the T-shaped zeolite membrane through hydrothermal crystallization;(2) sealing the synthesized T-shaped zeolite membrane, and dehydrating and separating the bio-oil by adopting a pervaporation process;(3) and (3) regenerating the T-shaped zeolite membrane polluted by the biological oil in the separation process of the step (2), and recycling the T-shaped zeolite membrane for dehydration and separation of the biological oil after the performance is recovered.
- 2. The method of claim 1, wherein SiO is present in the synthesis liquid precursor of step (1)2:Al2O3:Na2O:K2O:H2The molar ratio of O is 1 (0.04-0.06), (0.20-0.30), (0.05-0.15) and (35-60); the temperature of the hydrothermal crystallization is 150-180 ℃; the hydrothermal crystallization time is 2-10 h.
- 3. The method as claimed in claim 1, wherein the sealing in step (2) is performed by sealing one end of the T-shaped zeolite membrane with a polytetrafluoroethylene tube and connecting the other end with a vacuum pipeline.
- 4. The method of claim 1, wherein the feed side pressure in the pervaporation process of step (2) is atmospheric pressure and the permeate side pressure is vacuum.
- 5. The method according to claim 1, wherein the feed temperature in the pervaporation process of step (2) is 10-90 ℃.
- 6. The method of claim 1, wherein the bio-oil of step (2) is prepared from lignocellulose by rapid thermal cracking; the water content of the bio-oil is 10-40 wt%, and the pH value is 1-3.
- 7. The method as claimed in claim 1, wherein the process conditions for dehydration separation of bio-oil using the regenerated T-type zeolite membrane in step (3) are the same as those in step (2).
- 8. The method as claimed in claim 1, wherein the regeneration of the T-type zeolite membrane in step (3) comprises the steps of: firstly, soaking the T-shaped zeolite membrane polluted by the bio-oil in ethanol/water solution at normal temperature for cleaning, then drying the cleaned T-shaped zeolite membrane, and then placing the dried T-shaped zeolite membrane in a muffle furnace for roasting to obtain the regenerated T-shaped zeolite membrane.
- 9. The method according to claim 8, wherein the concentration of ethanol in the ethanol/water solution is 40-90 wt%, the soaking time is 6-12 h, and the soaking times are 1-5 times.
- 10. The method according to claim 8, wherein the roasting temperature is 100-260 ℃, the roasting time is 6-12 h, and the heating and cooling rate is 0.5-1 ℃/min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255347A (en) * | 2008-04-03 | 2008-09-03 | 浙江大学 | Method for preparing bio-diesel by immobilized lipase-water perselective membrane bioreactor |
| CN102021207A (en) * | 2010-11-04 | 2011-04-20 | 清华大学 | On-line dehydration process for preparing biodiesel from renewable grease through catalysis of lipase |
| CN102225313A (en) * | 2011-03-30 | 2011-10-26 | 大连理工大学 | Preparation method of mordenite membranes used for acetic acid dehydrating |
| US20130064747A1 (en) * | 2011-04-04 | 2013-03-14 | Georgia Tech Research Corporation | Zeolite ddr membranes |
| US20130067803A1 (en) * | 2011-09-20 | 2013-03-21 | Conocophillips Company | Advanced cellulosic renewable fuels |
| US20160090332A1 (en) * | 2014-09-30 | 2016-03-31 | Exxonmobil Chemical Patents Inc. | Production of Aromatics from Methanol and Co-Feeds |
| CN107848939A (en) * | 2015-06-10 | 2018-03-27 | 麦兰特公司 | The novel method of production acrylic acid using acetaldehyde as Main By product |
| CN109370666A (en) * | 2018-11-30 | 2019-02-22 | 华南理工大学 | A kind of separation method for bio oil high-efficiency dehydration |
-
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- 2019-12-16 CN CN201911296179.9A patent/CN111054217B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255347A (en) * | 2008-04-03 | 2008-09-03 | 浙江大学 | Method for preparing bio-diesel by immobilized lipase-water perselective membrane bioreactor |
| CN102021207A (en) * | 2010-11-04 | 2011-04-20 | 清华大学 | On-line dehydration process for preparing biodiesel from renewable grease through catalysis of lipase |
| CN102225313A (en) * | 2011-03-30 | 2011-10-26 | 大连理工大学 | Preparation method of mordenite membranes used for acetic acid dehydrating |
| US20130064747A1 (en) * | 2011-04-04 | 2013-03-14 | Georgia Tech Research Corporation | Zeolite ddr membranes |
| US20130067803A1 (en) * | 2011-09-20 | 2013-03-21 | Conocophillips Company | Advanced cellulosic renewable fuels |
| US20160090332A1 (en) * | 2014-09-30 | 2016-03-31 | Exxonmobil Chemical Patents Inc. | Production of Aromatics from Methanol and Co-Feeds |
| CN107848939A (en) * | 2015-06-10 | 2018-03-27 | 麦兰特公司 | The novel method of production acrylic acid using acetaldehyde as Main By product |
| CN109370666A (en) * | 2018-11-30 | 2019-02-22 | 华南理工大学 | A kind of separation method for bio oil high-efficiency dehydration |
Non-Patent Citations (2)
| Title |
|---|
| HANZHOU 等: ""Ultrathin zeolite X membranes for pervaporation dehydration of ethanol"", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 徐子雄 等: ""T 型分子筛膜的制备及异丙醇脱水应用"", 《硅 酸 盐 学 报》 * |
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