CN1916135A - Method for producing fuel oil from biological grease - Google Patents
Method for producing fuel oil from biological grease Download PDFInfo
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- CN1916135A CN1916135A CN 200610032222 CN200610032222A CN1916135A CN 1916135 A CN1916135 A CN 1916135A CN 200610032222 CN200610032222 CN 200610032222 CN 200610032222 A CN200610032222 A CN 200610032222A CN 1916135 A CN1916135 A CN 1916135A
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Abstract
This invention discloses a method for producing fuel oil from biogrease. The method comprises: (1) cracking biogrease, or a mixture of biogrease and catalytically cracking raw material, or a mixture of biogrease and catalytic gasoline in the presence of solid acid catalyst to obtain a mixture of liquefied gas, gasoline and diesel oil; (2) distilling the mixture and separating to obtain liquefied gas, gasoline and diesel oil products. The total yield of liquefied gas, gasoline and diesel oil is up to 88-92 wt.%, the content of propene in the liquefied gas is higher than 40 wt.%, and the octanr number of the gasoline is higher than 95. The method has simple process, and the products have a stable structure, thus providing a new way to utilize biological energy.
Description
One, technical field:
The present invention relates to a kind of method of producing oil fuel, particularly relate to a kind of bio-oil is produced oil fuel through catalytic pyrolysis method by bio-oil.
Two, background technology:
Along with fast development of society, world today's petroleum resources are exhausted day by day, so the research and development of the utilization of new forms of energy and energy utilization new way more and more are subjected to common concern.Major ingredient in the bio-oil is " tri-glyceride " (being neutral oil), accounts for more than 95% of total amount.All the other also contain: moisture, impurity, free fatty acids, protein, carbohydrate, deep and remote alcohol, pigment, hydro carbons, Fatty Alcohol(C12-C14 and C12-C18), wax and phosphatide, VITAMIN etc., also contain trace element: copper, iron, manganese, arsenic, mercury, phosphorus, sodium, zinc, nickel and lead etc.Elementary composition from bio-oil outside the above-mentioned element of eliminating minute, mainly contains C, H, O element, and be similar with the composition of oil, so the comprehensive utilizating research of bio-oil receives much concern.Present stage, the utilization of bio-oil research mainly concentrated on from bio-oil, extract vapour, diesel oil.
Introduced a kind of method of extracting petrol and diesel oil from the vegetable oil residue material among the CN1101067A, at first the oil foot material has been carried out the acidifying dehydration, thermo-cracking obtains thick oil in tank reactor again, thick oil is distilled to obtain gasoline, diesel oil then.This method exists complex process, long flow path, yield low, the problem that environmental pollution is serious.
Three, summary of the invention:
The objective of the invention is to propose that a kind of technology is simple, yield is high, environmental friendliness, directly bio-oil produced the method for oil fuel through catalytic pyrolysis.
The objective of the invention is to be achieved through the following technical solutions, a kind of method of producing oil fuel by bio-oil, it is characterized in that: directly be that raw material or bio-oil and catalytically cracked material are mixed into raw material or bio-oil and catalytic gasoline and are mixed into raw material with the bio-oil, catalytic cracking reaction takes place in the reactor of solid acid catalyst is housed, the catalytic cracking reaction temperature is 300～700 ℃, agent-oil ratio is 3.0～10.0, and weight space velocity is 5.0～20.0h
-1, the mix products behind the catalytic pyrolysis obtains liquefied gas, gasoline, diesel product through fractionation by distillation.
Described bio-oil comprises the tankage after Vegetable oil lipoprotein, animal grease and the bio-oil refining.Vegetable oil lipoprotein is meant herbaceous plant oil, xylophyta oil or their mixture.Herbaceous plant oil is meant soybean oil, peanut oil, rapeseed oil, sunflower seed oil, Oleum Gossypii semen or their mixture.Xylophyta oil is meant brown tung oil, Oleum Cocois, walnut oil, grease, camellia seed oil or their mixture.Animal grease is meant lard, butter, sheep oil, chicken fat, duck oil, whale oil, fish oil or their mixture.Tankage after the bio-oil refining also can be described as bio-oil.
Described catalytically cracked material is meant 350～500 ℃ vacuum distillate, long residuum and vacuum residuum, or the wax tailings of secondary processing, the sweat oil behind the lubricating oil dewaxing, diasphaltene and raffinate oil etc. and to meet the raw material that the charging of plant catalytic cracking unit requires.
Described bio-oil and catalytically cracked material blended weight percent are 0～100%.
Described bio-oil and catalytic gasoline blended weight percent are 0～100%.
Described solid acid catalyst is made up of molecular sieve, carrier and binding agent.Molecular sieve comprises Y zeolite, ZSM-5 molecular sieve or its mixture.Y zeolite comprises REY, USY, REUSY and metal thereof and nonmetal modified molecular screen.The ZSM-5 molecular sieve comprises the ZSM-5 molecular sieve analog of organic amine and the preparation of inorganic amine synthesis method, and silica alumina ratio also comprises the ZSM-5 molecular sieve that adopts metal or nonmetal modification in 20～160 scopes.Carrier comprises kaolin, halloysite, activated alumina or its mixture.Binding agent comprises silicon sol, aluminium colloidal sol, silica-alumina gel and composition thereof.Solid acid catalyst can be microspheric, stripe shape, granular, cylinder shape.
Described catalytic cracking reaction can carry out in fluidized-bed, moving-bed or fixed-bed reactor, and described fractionation by distillation can adopt the method for compression, distillation, rectifying.
The present invention has not only widened the purposes of bio-oil, a bio-oil is provided and has been refined into the tankage production new technology that produces in the edible oil process, main is for the oil supply that relaxes growing tension provides an energy utilization new way, also provides a new way for biological derived energy chemical and combining of modern petrochemical complex.The mass percent of the liquefied gas that is obtained by the present invention, gasoline, diesel oil sum can reach 88～92%, the weight percent of propylene content can reach more than 40% in the liquefied gas, and gasoline research method octane value is more than 95, and technology is simple, flow process is short, and environmental pollution is little.
Four, embodiment:
The present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1:
Adopt the preparation method of conventional refining catalytic cracking catalyst to prepare catalyzer, REUSY molecular sieve, kaolin, aluminium colloidal sol, aluminum oxide are mixed making beating evenly with a certain amount of water after, carry out the press atomization moulding and obtain microspheric catalyst.
Catalyzer 40～200 mesh sieves of getting above-mentioned preparation divide 300 grams, carry out hydrothermal aging and handle on fluidized-bed, and condition is 800 ℃, 100% water vapour.Get catalyzer after the 120g hydrothermal treatment consists and pack in the fluidized-bed reactor, bubbling air carries out fluidisation, is warming up to 470 ℃ of constant temperature, feed water vapour and remove air, guarantee catalyst fluidization simultaneously, when improving bed temperature then and reaching 500 ℃, refined rapeseed oil charging 20g, weight space velocity 16.0h
-1, contacting with the fluidizing catalyzer and to carry out catalytic cracking reaction, agent-oil ratio is 6.0.After treating that scission reaction is finished, feed water vapour and carried out stripping 20 minutes,, reduce coke and generate so that make the timely desorption of partial reaction product that is adsorbed on the catalyzer.Be warmed up to 620 ℃, cut off water vapour, aerating oxygen is regenerated.Gas adopts the drainage metering to collect after the scission reaction, and liquid ingredient is collected after condensation, Weighing, and regenerated flue gas is collected with airbag.
The reacted gas of collecting is analyzed on 5890-II type gas chromatograph.Regenerated flue gas is analyzed on infrared flue gas instrument.The liquid mixing product adopts SP-3400 type gas chromatograph to analyze, and determines components contents such as liquefaction vapour, gasoline, diesel oil, and the product distribution results sees Table 1.The liquid mixing product is sent to rectifying, and the gasoline that obtains is analyzed on 5890-II type gas chromatograph, and group composition obtains octane value according to gasoline octane rating, and gasoline family's composition and research octane number (RON), motor-method octane number see Table 2.
Embodiment 2:
The rapeseed oil charging is 20g, and agent-oil ratio is 6.0, weight space velocity 16h
-1, 520 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1, table 2.
Embodiment 3:
The soybean oil charging is 16g, and agent-oil ratio is 10.0, weight space velocity 16.0h
-1, 520 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1, table 2.
Embodiment 4
Catalyzer adopts catalytic cracking unit REUSY class poiser, need not carry out hydrothermal treatment consists, and the Oleum Gossypii semen charging is 20g, and agent-oil ratio is 6.0, weight space velocity 16h
-1, 500 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1, table 2.
Embodiment 5
The preparation method of refining catalytic cracking catalyst adopts REUSY and ZSM-5 composite molecular screen to prepare catalyzer routinely, and the rapeseed oil charging is 20g, and agent-oil ratio is 6.0, weight space velocity 16h
-1, 520 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1, table 2.
Embodiment 6:
Catalyzer adopts catalytic cracking unit REUSY class poiser, need not carry out hydrothermal treatment consists, and the tankage charging that the vegetable seed refining process produces is 24g, and agent-oil ratio is 3.0, weight space velocity 5.0h
-1, 520 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1, table 2.
Embodiment 7:
Preparation of Catalyst adopts and rolls the extrusion method, with REUSY molecular sieve, kaolin, aluminium colloidal sol, aluminum oxide and a certain amount of water, behind the mechanical mixing, sends into rolling machine earlier, fully rolls mixing, is squeezed into strip by banded extruder then.Be divided into 2-3nm after the roasting of extrusion gained catalyzer, wear out at the fixed bed aging equipment: condition is 800 ℃, 100% water vapour.
Get catalyzer after the 4g hydrothermal treatment consists and pack in the fixed-bed reactor, under nitrogen atmosphere, elevated temperature to 300 ℃ after bed temperature is stable, enters step of reaction, rapeseed oil inlet amount 3g, and 75 seconds oil-feed time reaction back is carried 20 minutes with nitrogen gas.Reacted gas is formed with online stratographic analysis.The liquid receiving portions goes out gasoline, diesel oil, heavy oil with the simulation distil stratographic analysis.Enter the regeneration stage after the reaction, 550 ℃ of temperature, 20 minutes time, flue gas analyzes C content with infrared analyzer, the results are shown in Table 1,2.
Embodiment 8:
Catalyzer adopts catalytic cracking unit REUSY class poiser, need not carry out hydrothermal treatment consists, 1: 1 mixed of the weight ratio that rapeseed oil charging and wax tailings are pressed, and the reaction combined feed total feed is 20g, agent-oil ratio is 6.0, weight space velocity 20.0h
-1, 520 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1,2.
Embodiment 9
Catalyzer adopts catalytic cracking unit REUSY class poiser, need not carry out hydrothermal treatment consists, and rapeseed oil charging and catalytic gasoline are pressed 50m%: the 50m% mixed, and the reaction combined feed total feed is 20g, agent-oil ratio is 6.0, weight space velocity 20.0h
-1, 520 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1,2.
Embodiment 10:
Catalyzer adopts catalytic cracking unit REUSY class poiser, need not carry out hydrothermal treatment consists, 1: 1 mixed of the weight ratio that rapeseed oil charging and catalytic gasoline are pressed, and the reaction combined feed total feed is 20g, agent-oil ratio is 6.0, weight space velocity 20.0h
-1, 700 ℃ of temperature of reaction, other is with embodiment 1.The results are shown in Table 1,2.
The product of table 1, liquid mixing product distributes
Table 2, gasoline family's composition and research octane number (RON), motor-method octane number
| Embodiment 5 | 1.11 | 2.81 | 22.50 | 1.53 | 71.98 | 101.3 | 78.6 |
| Embodiment 6 | 1.97 | 10.34 | 18.90 | 4.53 | 63.79 | 96.5 | 77.0 |
| Embodiment 7 | 4.56 | 12.93 | 13.83 | 5.20 | 63.01 | 94.4 | 76.4 |
| Embodiment 8 | 3.14 | 13.44 | 8.66 | 5.11 | 69.44 | 98.7 | 80.0 |
| Embodiment 9 | 3.02 | 15.05 | 19.06 | 6.77 | 55.47 | 93.7 | 76.3 |
| Embodiment 10 | 3.21 | 14.68 | 11.98 | 6.55 | 63.58 | 93.7 | 76.3 |
Claims (7)
1, a kind of method of producing oil fuel by bio-oil, it is characterized in that: directly be that raw material or bio-oil and catalytically cracked material are mixed into raw material or bio-oil and catalytic gasoline and are mixed into raw material with the bio-oil, catalytic cracking reaction takes place in the reactor of solid acid catalyst is housed, the catalytic cracking reaction temperature is 300～700 ℃, agent-oil ratio is 3～10, and weight space velocity is 5～20h
-1, the mix products behind the catalytic pyrolysis obtains liquefied gas, gasoline, diesel product through fractionation by distillation.
2, method according to claim 1 is characterized in that: described bio-oil comprises the tankage after Vegetable oil lipoprotein, animal grease and the bio-oil refining.
3, method according to claim 1 is characterized in that: described bio-oil and catalytically cracked material blended mass percent are 0～100%.
4, method according to claim 1 is characterized in that: described bio-oil and catalytic gasoline blended mass percent are 0～100%.
5, method according to claim 1 is characterized in that: described solid acid catalyst is made up of molecular sieve, carrier and binding agent.
6, method according to claim 1 is characterized in that: 400～600 ℃ more fortunately of described scission reaction temperature.
7, method according to claim 1 is characterized in that: described fractionation by distillation can adopt the method for compression, distillation, rectifying.
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|---|---|---|---|
| CN 200610032222 CN1916135A (en) | 2006-09-06 | 2006-09-06 | Method for producing fuel oil from biological grease |
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| CN 200610032222 CN1916135A (en) | 2006-09-06 | 2006-09-06 | Method for producing fuel oil from biological grease |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457149B (en) * | 2007-12-14 | 2013-01-02 | 周鼎力 | Method for producing gasoline and diesel oil by lipid |
| CN102942952A (en) * | 2012-10-07 | 2013-02-27 | 青岛科技大学 | Method for preparing liquid fuel oil via catalytic cracking of biological oil and fat with USY as catalyst |
| CN103194255A (en) * | 2013-04-18 | 2013-07-10 | 方建华 | Method for producing clean fuels by catalyzing and cracking animal and vegetable oil |
| CN106890663A (en) * | 2017-03-31 | 2017-06-27 | 青岛科技大学 | The method that the mesopore molecular sieve catalytic pyrolysis bio-oils of novel alkaline MNC 13 prepare liquid-fuel oil |
| CN110437872A (en) * | 2019-09-03 | 2019-11-12 | 四川润和催化新材料股份有限公司 | A method of improving oil quality using bio oil catalytic cracking and improves yield of light olefins |
| WO2021043018A1 (en) * | 2019-09-03 | 2021-03-11 | 四川润和催化新材料股份有限公司 | Method for improving quality of oil product and increasing yield of low carbon olefin using catalytic cracking of bio-oil |
-
2006
- 2006-09-06 CN CN 200610032222 patent/CN1916135A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457149B (en) * | 2007-12-14 | 2013-01-02 | 周鼎力 | Method for producing gasoline and diesel oil by lipid |
| CN102942952A (en) * | 2012-10-07 | 2013-02-27 | 青岛科技大学 | Method for preparing liquid fuel oil via catalytic cracking of biological oil and fat with USY as catalyst |
| CN103194255A (en) * | 2013-04-18 | 2013-07-10 | 方建华 | Method for producing clean fuels by catalyzing and cracking animal and vegetable oil |
| CN103194255B (en) * | 2013-04-18 | 2015-08-12 | 方建华 | Catalytic cracking animal-plant oil produces the method for clean fuel |
| CN106890663A (en) * | 2017-03-31 | 2017-06-27 | 青岛科技大学 | The method that the mesopore molecular sieve catalytic pyrolysis bio-oils of novel alkaline MNC 13 prepare liquid-fuel oil |
| CN106890663B (en) * | 2017-03-31 | 2019-08-13 | 青岛科技大学 | The method of novel alkaline MNC-13 mesopore molecular sieve catalytic pyrolysis bio-oil liquid fuel was prepared oil |
| CN110437872A (en) * | 2019-09-03 | 2019-11-12 | 四川润和催化新材料股份有限公司 | A method of improving oil quality using bio oil catalytic cracking and improves yield of light olefins |
| WO2021043018A1 (en) * | 2019-09-03 | 2021-03-11 | 四川润和催化新材料股份有限公司 | Method for improving quality of oil product and increasing yield of low carbon olefin using catalytic cracking of bio-oil |
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