CN109628143B - Method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil - Google Patents
Method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil Download PDFInfo
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil; the method comprises the steps of cracking biomass in a fast pyrolysis device to obtain raw biomass oil, carrying out mild hydrogenation on the raw biomass oil, mixing the raw biomass oil with refined wax oil (obtained after straight-run wax oil is hydrogenated) according to a certain proportion, further carrying out co-refining in a catalytic cracking device, carrying out hydrogenation upgrading on the obtained catalytic diesel oil and catalytic gasoline in a catalytic diesel oil hydrogenation device and a catalytic gasoline hydrogenation device respectively, and finally obtaining diesel oil and gasoline products meeting national standards. The existing production and processing equipment of refineries can be utilized to greatly reduce the investment cost of biological refineries, so that the production cost of biomass gasoline and diesel can be reduced; the quality of the biomass gasoline and diesel oil can meet the national standard by utilizing the existing blending device of a refinery; finally, the problem of consumption of the biomass gasoline and diesel can be effectively solved by utilizing a distribution system of a refinery.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of biomass utilization, and particularly relates to a method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil.
[ background of the invention ]
Due to the heavy and inferior crude oil, the increasing demand of gasoline and diesel oil and the increasing quality of gasoline and diesel oil, considering the characteristics of sulfur and nitrogen free of biological gasoline and diesel oil and the attribute of green energy, how to put biological gasoline and diesel oil into the market becomes a research hotspot. However, the investment cost of biomass raw materials and biorefineries is high, and the biodiesel is only a certain fraction of petroleum-based gasoline and diesel, and needs to be further blended, so that the production cost of the biodiesel is far higher than that of the petroleum-based gasoline and diesel. Therefore, how to greatly reduce the production cost of the biodiesel and meet the national quality requirements of the biodiesel is a main focus of current research and development of the biodiesel.
If the biomass oil and the crude oil are mixed and refined together in a refinery (hereinafter, the mixture is referred to as co-refining), the existing production processing device of the refinery can be directly utilized to greatly reduce the investment cost; secondly, blending the co-refined product in a refinery directly to meet the national standard, and saving the transportation cost of blending the biodiesel; finally, the distribution system of the refinery can effectively solve the problem of the consumption of the biodiesel. Therefore, the co-refining of the biomass oil and the crude oil in the refinery can effectively solve the problems of the biodiesel.
The co-refining process of the fast pyrolysis biomass oil and the straight-run wax oil is theoretically feasible through reference of literature, however, the application of the technology in the actual industrial process is unclear, such as the organization of the process flow, the control of the hydrogenation depth of the biomass oil and the like.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a process flow for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil; the process comprises the steps of cracking the wood biomass into biomass oil in a fast pyrolysis device, hydrogenating the biomass oil, mixing the biomass oil with refined wax oil, and refining the mixture in a catalytic cracking device to obtain gasoline products and diesel oil products which meet the national standard.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil comprises the following steps:
step 1, reacting wood biomass in a fast pyrolysis device to obtain biomass oil;
step 2, removing oxygen-containing impurities from the fast pyrolysis biomass oil through a hydrogenation device to prepare hydrogenated biomass oil;
step 3, converting the straight-run wax oil into refined wax oil through a wax oil hydrogenation device;
step 4, mixing refined wax oil and hydrogenated biomass oil to form a mixture, wherein the mass ratio of the refined wax oil is 80-95%, and the mass ratio of the hydrogenated biomass oil is 5-20%; the mixture is refined in a catalytic cracking device together, and meanwhile, catalytic diesel oil with biomass and catalytic gasoline with biomass are obtained;
step 5, removing impurities from the catalytic diesel oil obtained in the step 4 in a catalytic diesel oil hydrogenation device to obtain a diesel oil product containing biomass; and (4) removing impurities from the catalytic gasoline obtained in the step (4) in a catalytic gasoline hydrogenation device to obtain a gasoline product containing biomass.
The invention is further improved in that:
preferably, in step 1, the woody biomass is pyrolyzed in a fast pyrolysis unit; the pyrolysis reaction temperature is 500-550 ℃, and the pyrolysis time is 1.5-2.5 s.
Preferably, in the step 1, the yield of the obtained biomass oil is 50-60%, and the oxygen content in the biomass oil is 35-45%.
Preferably, in the step 2, the fast pyrolysis oil hydrogenation device is provided with two sections of hydrogenation reactors; the reaction temperature of the first-stage hydrogenation reactor is 140-180 ℃, the reaction pressure is 7.5-8.5 MPa, the reaction temperature of the second-stage hydrogenation reactor is 180-250 ℃, and the reaction pressure is 13-14 MPa.
Preferably, in the step 2, the liquid space velocity is 0.5h in the process of removing oxygen-containing impurities in the fast pyrolysis oil hydrogenation device-1The biomass fuel consumption per cubic meter is 250-350 Nm3。
Preferably, in the step 2, the oxygen content of the prepared hydrogenated biomass oil is 15-25%.
Preferably, in the step 4, when the mixture is refined in the catalytic cracking device, the reaction temperature is 490-520 ℃, and the reaction pressure is 0.1-0.2 MPa.
Preferably, in the step 5, the reaction temperature of the catalytic diesel hydrogenation device is 290-340 ℃, the reaction pressure is 6-8 MPa, and the space velocity is 2-2.5 h-1。
Preferably, in the step 5, the reaction temperature of the gasoline oil hydrogenation catalytic device is 240-300 ℃, the reaction pressure is 2-2.3 MPa, and the space velocity is 2.5-3 h-1。
Preferably, the oxygen content in the diesel oil containing the biomass and the oxygen content in the gasoline containing the biomass, which are prepared in the step 5, are both less than or equal to 2.7 percent.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil; according to the method, biomass oil is pyrolyzed in a fast pyrolysis device, and is mixed with refined wax oil (after straight-run wax oil is hydrogenated) according to a certain proportion after being subjected to mild hydrogenation, so that the mixture is refined in a catalytic cracking device, the obtained catalytic diesel oil and catalytic gasoline are respectively hydrogenated and upgraded in a catalytic diesel oil hydrogenation device and a catalytic gasoline hydrogenation device, and finally, diesel oil and gasoline products meeting national standards can be obtained. The investment cost of a biological refinery can be greatly reduced by utilizing the existing production and processing equipment of the refinery, so that the production cost of the biomass gasoline and diesel can be reduced; the quality of the biomass gasoline and diesel oil can meet the national standard by utilizing the existing blending device of a refinery; finally, the problem of consumption of the biomass gasoline and diesel can be effectively solved by utilizing a distribution system of a refinery. Therefore, the process can effectively reduce the production cost of the biodiesel, effectively solve the problem of consumption of the biodiesel and provide guidance for the biomass fuel to rapidly enter the market.
[ description of the drawings ]
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a material balance diagram of example 1 of the present invention;
FIG. 3 is a material balance diagram of example 2 of the present invention;
FIG. 4 is a material balance diagram of example 3 of the present invention;
FIG. 5 is a material balance diagram of example 4 of the present invention;
FIG. 6 is a material balance diagram of example 5 of the present invention.
[ detailed description ] embodiments
The invention is further described in detail with reference to the accompanying drawings and specific steps, and discloses a method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil, and referring to fig. 1, the method specifically comprises the following steps:
step 1, carrying out pyrolysis reaction on the collected woody biomass in a rapid pyrolysis device, wherein the pyrolysis reaction temperature is 500-550 ℃, the retention time is 1.5-2.5 s, the yield of the finally obtained biomass oil is 45-60%, and the oxygen content in the biomass oil is 35-45%.
Step 2, removing oxygen-containing impurities from the fast pyrolysis biomass oil prepared in the step 1 in a fast pyrolysis oil hydrogenation device through reaction with hydrogen so as to improve the stability and quality of the biomass oil and prepare hydrogenated biomass oil; the hydrogenation device is provided with two-stage hydrogenation reactors, wherein the reaction temperature of the first-stage hydrogenation reactor is 140-180 ℃, the pressure is 7.5-8.5 MPa, the reaction temperature of the second-stage hydrogenation reactor is 180-250 ℃, the pressure is 13-14 MPa, and the liquid space velocity is 0.5-1 h-1The biomass fuel consumption per cubic meter in the whole process is 250-350 Nm3And finally controlling the oxygen content of the hydrogenated biomass oil to be 15-25%.
Step 3, preparing refined wax oil from straight-run wax oil extracted from an atmospheric and vacuum distillation unit of a refinery after passing through a wax oil hydrogenation unit, and mixing the refined wax oil and hydrogenated biomass oil according to a mass ratio, wherein the hydrogenated biomass oil accounts for 5-20% of the mass ratio, and the rest is refined wax oil accounting for 80-95%; and (2) co-refining the mixture in a catalytic cracking device, wherein the reaction temperature of the catalytic cracking device is 490-520 ℃, and the pressure of the catalytic cracking device is 0.1-0.2 MPa, so that catalytic diesel oil and catalytic gasoline are obtained simultaneously, 4-18% of carbon source biomass in the catalytic diesel oil and the catalytic gasoline is obtained, the yield of the catalytic diesel oil is 16-24%, and the yield of the catalytic gasoline is 50-60%.
Step 4, respectively hydrogenating and refining the catalytic diesel oil and the catalytic gasoline obtained in the step 3 in an existing catalytic diesel oil hydrogenation device and a catalytic gasoline hydrogenation device of a refinery to remove impurities containing sulfur, oxygen and the like, wherein the reaction temperature in the catalytic diesel oil hydrogenation process is 290-340 ℃, the pressure is 6-8 MPa, and the space velocity is 2-2.5 h-1(ii) a The reaction temperature of the catalytic gasoline hydrogenation process is 240-300 ℃, the pressure is 2-2.3 MPa, and the space velocity is 2.5-3 h-1. Finally, the diesel oil and the gasoline which meet the national standard in quality and contain biomass can be obtained, and the oxygen content of the diesel oil and the gasoline is not more than 2.7 percent.
Example 1
Before the co-refining technology is applied, the proportion of the catalytic cracking unit and the biomass oil co-refining is preferably selected, and the embodiment is illustrated when the processing amount of the catalytic cracking unit with 120 ten thousand tons of processing capacity of a certain refinery year and the proportion of the co-refining is 19%, and the material balance diagram is shown in FIG. 2:
(1) through calculation, the biomass feeding flow rate of the fast pyrolysis device is 83.93t/h, 39.03t/h of biomass oil is obtained after pyrolysis, the yield is 46.5%, the reactor inlet temperature of the device is 500 ℃, the retention time is 1.8s, and the oxygen content in the biomass oil is 45%.
(2) 39.03t/h of biomass oil obtained by a fast pyrolysis device is subjected to hydrodeoxygenation by a biomass oil hydrogenation device to obtain hydrogenated biomass oil 25.68t/h, the yield is 65.8 percent, the reaction temperature of a first-stage hydrogenation reactor of the device is 140 ℃, the pressure is 8.3MPa, the reaction temperature of a second-stage hydrogenation reactor is 180 ℃, the pressure is 13.8MPa, and the liquid airspeed of the two reactors is 0.5h-1(ii) a The fuel consumption of the biomass per cubic meter in the whole process is 260Nm3(ii) a And the oxygen content of the biomass oil after final hydrogenation is controlled to be 25%.
(3) And (3) fractionating 505.6t/h of crude oil by an atmospheric and vacuum distillation device to obtain 114.16t/h of straight-run wax oil.
(4)114.16t/h straight-run wax oil passes through a wax oil hydrogenation device to obtain 109.59t/h refined wax oil, the yield is 96%, the reaction temperature of the wax oil hydrogenation device is 370 ℃, the pressure is 10.8MPa, and the space velocity is 1h-1。
(5) After 25.68t/h (19%) of hydrogenated biomass oil and 109.59t/h (81%) of refined wax oil are mixed, the mixture enters a catalytic cracking device with the annual processing amount of 120 ten thousand tons for co-refining, the biomass oil accounts for 19% of the total feed, the reaction temperature of the catalytic cracking device is 490 ℃, and the pressure is 0.2 MPa; finally, 31.55t/h of catalytic diesel oil and 68.82t/h of catalytic gasoline are obtained, the yield of the diesel oil is 23.3 percent, and the yield of the gasoline is 50.9 percent.
(6) Refining 31.55t/h of catalytic diesel in a diesel hydrogenation device, wherein the reaction temperature of the hydrogenation device is 313 ℃, the pressure is 7.05MPa, and the space velocity is 2.5h-1(ii) a Finally, a diesel product of 26.76t/h and a gasoline product of 3.72t/h are obtained, the liquid yield is 96.6 percent, wherein the diesel yield is 84.8 percent, and the gasoline yield is 11.8 percent.
(7) Cracking the catalyst68.82t/h catalytic gasoline obtained by the conversion device is refined in a gasoline hydrogenation device, the reaction temperature is 258 ℃, the pressure is 2.1MPa, and the space velocity is 2.6h-1(ii) a Finally obtaining the gasoline product with 68.13t/h and the yield of 99 percent.
Example 2
The catalytic cracking unit with a processing capacity of 200 ten thousand tons per year in a certain refinery and the biomass oil co-refining proportion of 10% are explained, and the material balance diagram is shown in fig. 3:
(1) the biomass feeding flow rate of the fast pyrolysis device is 72.15t/h, biomass oil of 36.08t/h is obtained after pyrolysis, the yield is 50%, the reactor inlet temperature of the device is 510 ℃, the retention time is 1.9s, and the oxygen content in the biomass oil is 43%.
(2) The 36.08t/h of biomass oil obtained by the rapid pyrolysis device is subjected to hydrodeoxygenation by a biomass oil hydrogenation device to obtain hydrogenated biomass oil 23.81t/h, the yield is 66%, the reaction temperature of a first-stage hydrogenation reactor of the device is 150 ℃, the pressure is 8.5MPa, the reaction temperature of a second-stage hydrogenation reactor is 200 ℃, the pressure is 14MPa, and the liquid airspeed of the two-stage reactors is 0.5h-1(ii) a The hydrogen consumption of biomass per cubic meter in the whole process is 295Nm3(ii) a And the oxygen content of the biomass oil after final hydrogenation is controlled to be 20%.
(3)965.47t/h crude oil is fractionated by an atmospheric and vacuum distillation device to obtain 222.06t/h straight-run wax oil.
(4)222.06t/h straight-run wax oil passes through a wax oil hydrogenation device to obtain 214.29t/h refined wax oil, the yield is 96.5%, the reaction temperature of the wax oil hydrogenation device is 380 ℃, the pressure is 10.5MPa, and the space velocity is 1h-1。
(5) After 23.81t/h (10%) of hydrogenated biomass oil and 214.29t/h (90%) of refined wax oil are mixed, the mixture enters a catalytic cracking device with the annual processing amount of 200 ten thousand tons for co-refining, the biomass oil accounts for 10% of the total feed, the reaction temperature of the catalytic cracking device is 500 ℃, and the pressure is 0.16 MPa; finally obtaining 40.48t/h of catalytic diesel oil and 130.95t/h of catalytic gasoline, wherein the yield of the diesel oil is 17 percent and the yield of the gasoline is 55 percent.
(6) Refining 40.48t/h of catalytic diesel oil in a diesel oil hydrogenation device, wherein the reaction temperature of the hydrogenation device303 ℃, the pressure of 7.3MPa and the space velocity of 2.5h-1(ii) a Finally obtaining 36.43t/h diesel oil product and 3.24t/h gasoline product, wherein the liquid yield is 98 percent, the diesel oil yield is 90 percent, and the gasoline yield is 8 percent.
(7) 130.95t/h catalytic gasoline obtained by a catalytic cracking device is refined in a gasoline hydrogenation device, the reaction temperature is 260 ℃, the pressure is 2.2MPa, and the space velocity is 2.5h-1(ii) a Finally obtaining 129.64t/h gasoline product with the yield of 99 percent.
Example 3
The catalytic cracking unit with 80 ten thousand tons of processing capacity per year of a refinery and the biomass oil co-refining proportion of 5 percent are explained, and the material balance diagram is shown in fig. 4:
(1) the biomass feeding flow rate of the fast pyrolysis device is 13.02t/h, 6.90t/h of biomass oil is obtained after pyrolysis, the yield is 53%, the reactor inlet temperature of the device is 550 ℃, the retention time is 1.5s, and the oxygen content in the biomass oil is 38%.
(2) 6.90t/h of biomass oil obtained by a fast pyrolysis device is subjected to hydrodeoxygenation by a biomass oil hydrogenation device to obtain hydrogenated biomass oil 4.76t/h with the yield of 69 percent, the reaction temperature of a first-stage hydrogenation reactor of the device is 145 ℃, the pressure is 8.2MPa, the reaction temperature of a second-stage hydrogenation reactor is 190 ℃, the pressure is 13.5MPa, and the liquid airspeeds of the two reactors are 0.5h-1(ii) a The hydrogen consumption of biomass per cubic meter in the whole process is 280Nm3(ii) a And the oxygen content of the biomass oil after final hydrogenation is controlled to be 20%.
(3)428.39t/h crude oil is fractionated by an atmospheric and vacuum distillation device to obtain 94.25t/h straight-run wax oil.
(4)94.25t/h of straight-run wax oil passes through a wax oil hydrogenation device to obtain 90.48t/h of refined wax oil, the yield is 96%, the reaction temperature of the wax oil hydrogenation device is 375 ℃, the pressure is 10.7MPa, and the space velocity is 1h-1。
(5) After 4.76t/h (5%) of hydrogenated biomass oil and 90.48t/h (95%) of refined wax oil are mixed, the mixture enters a catalytic cracking device with 80 ten thousand tons of annual processing amount to be co-refined, the biomass oil accounts for 5% of the total feed, the reaction temperature of the catalytic cracking device is 520 ℃, and the pressure is 0.1 MPa; finally, 17.14t/h of catalytic diesel oil and 55.24t/h of catalytic gasoline are obtained, the yield of the diesel oil is 18 percent, and the yield of the gasoline is 58 percent.
(6) Refining 17.14t/h of catalytic diesel in a diesel hydrogenation device, wherein the reaction temperature of the hydrogenation device is 300 ℃, the pressure is 7.3MPa, and the space velocity is 2.5h-1(ii) a Finally, a diesel product of 14.91t/h and a gasoline product of 1.71t/h are obtained, the liquid yield is 97 percent, wherein the diesel yield is 87 percent, and the gasoline yield is 10 percent.
(7) 55.24t/h catalytic gasoline obtained by a catalytic cracking device is refined in a gasoline hydrogenation device, the reaction temperature is 255 ℃, the pressure is 2.3MPa, and the space velocity is 2.5h-1(ii) a Finally 54.58t/h of gasoline product is obtained, and the yield is 98.8%.
Example 4
The explanation is given when the co-refining proportion of the catalytic cracking device and the biomass oil with the processing capacity of 80 ten thousand tons in a certain refinery year is 20 percent:
(1) the biomass feeding flow rate of the fast pyrolysis device is 64.23t/h, 28.9t/h of biomass oil is obtained after pyrolysis, the yield is 45%, the reactor inlet temperature of the device is 520 ℃, the retention time is 2.0s, and the oxygen content in the biomass oil is 40%.
(2) The 28.9t/h of biomass oil obtained by the rapid pyrolysis device is subjected to hydrodeoxygenation by a biomass oil hydrogenation device to obtain 19.05t/h of hydrogenated biomass oil, the yield is 65.9 percent, the reaction temperature of a first-stage hydrogenation reactor of the device is 180 ℃, the pressure is 7.8MPa, the reaction temperature of a second-stage hydrogenation reactor is 250 ℃, the pressure is 13MPa, and the liquid airspeed of the two-stage reactors is 0.8h-1(ii) a The hydrogen consumption of biomass per cubic meter in the whole process is 350Nm3(ii) a The oxygen content of the biomass oil after final hydrogenation is controlled at 15%.
(3)322.91t/h crude oil is fractionated by an atmospheric and vacuum distillation device to obtain 78.14t/h straight-run wax oil.
(4)78.14t/h straight-run wax oil passes through a wax oil hydrogenation device to obtain 76.19t/h refined wax oil, the yield is 96%, the reaction temperature of the wax oil hydrogenation device is 375 ℃, the pressure is 10.7MPa, and the space velocity is 1h-1。
(5) Mixing hydrogenated biomass oil 19.04t/h (20%) and refined wax oil 76.19t/h (80%), and co-refining in a catalytic cracking device with annual processing capacity of 80 ten thousand tons, wherein the biomass oil accounts for 20% of the total feed, the reaction temperature of the catalytic cracking device is 510 ℃, and the pressure is 0.13 MPa; finally, 15.24t/h of catalytic diesel oil and 57.14t/h of catalytic gasoline are obtained, the yield of the diesel oil is 16 percent, and the yield of the gasoline is 60 percent.
(6) Refining 15.24t/h of catalytic diesel in a diesel hydrogenation device, wherein the reaction temperature of the hydrogenation device is 290 ℃, the pressure is 6MPa, and the space velocity is 2h-1(ii) a Finally, a 13.26t/h diesel product and a 1.52t/h gasoline product are obtained, the liquid yield is 97%, wherein the diesel yield is 87%, and the gasoline yield is 10%.
(7) Refining 57.14t/h catalytic gasoline obtained by a catalytic cracking device in a gasoline hydrogenation device, wherein the reaction temperature is 240 ℃, the pressure is 2MPa, and the space velocity is 3h-1(ii) a Finally 56.51t/h of gasoline product is obtained, and the yield is 98.9%.
Example 5
The explanation is given when the co-refining proportion of the catalytic cracking device and the biomass oil of which the processing amount per year of a certain refinery is 80 ten thousand tons is 15%:
(1) the biomass feeding flow rate of the fast pyrolysis device is 34.51t/h, 20.7t/h of biomass oil is obtained after pyrolysis, the yield is 60%, the reactor inlet temperature of the device is 530 ℃, the retention time is 2.5s, and the oxygen content in the biomass oil is 35%.
(2) The 20.7t/h of biomass oil obtained by the rapid pyrolysis device is subjected to hydrodeoxygenation by a biomass oil hydrogenation device to obtain hydrogenated biomass oil 14.29t/h, the yield is 69 percent, the reaction temperature of a first-stage hydrogenation reactor of the device is 160 ℃, the pressure is 7.5MPa, the reaction temperature of a second-stage hydrogenation reactor is 240 ℃, the pressure is 13.2MPa, and the liquid airspeeds of the two reactors are all 1h-1(ii) a The hydrogen consumption of biomass per cubic meter in the whole process is 250Nm3(ii) a The oxygen content of the biomass oil after final hydrogenation is controlled to be 18 percent.
(3)351.73t/h crude oil is fractionated by an atmospheric and vacuum distillation device to obtain 84.06t/h straight-run wax oil.
(4)84.06t/h straight-run wax oil is subjected to wax oil addition80.95t/h of refined wax oil is obtained after the hydrogen device, the yield is 96.3 percent, the reaction temperature of the wax oil hydrogenation device is 375 ℃, the pressure is 10.7MPa, and the airspeed is 1h-1。
(5) After 14.29t/h (15%) of hydrogenated biomass oil and 80.95t/h (85%) of refined wax oil are mixed, the mixture enters a catalytic cracking device with 80 ten thousand tons of annual processing amount to be co-refined, the biomass oil accounts for 15% of the total feed, the reaction temperature of the catalytic cracking device is 500 ℃, and the pressure is 0.15 MPa; finally, 19.05t/h of catalytic diesel oil and 47.62t/h of catalytic gasoline are obtained, the yield of the diesel oil is 20 percent, and the yield of the gasoline is 50 percent.
(6) Refining 19.05t/h of catalytic diesel in a diesel hydrogenation device, wherein the reaction temperature of the hydrogenation device is 340 ℃, the pressure is 8MPa, and the space velocity is 2.2h-1(ii) a Finally, 17.39t/h of diesel oil product and 1.39t/h of gasoline product are obtained, the liquid yield is 98.6 percent, wherein the diesel oil yield is 91.3 percent, and the gasoline yield is 7.3 percent.
(7) 47.62t/h catalytic gasoline obtained by a catalytic cracking device is refined in a gasoline hydrogenation device, the reaction temperature is 330 ℃, the pressure is 2.3MPa, and the space velocity is 2.7h-1(ii) a Finally, 46.86t/h of gasoline product is obtained, and the yield is 98.4%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil is characterized by comprising the following steps:
step 1, reacting wood biomass in a fast pyrolysis device to obtain fast pyrolysis biomass oil;
step 2, removing oxygen-containing impurities from the fast pyrolysis biomass oil through a hydrogenation device to prepare hydrogenated biomass oil;
in the step 2, the fast pyrolysis oil hydrogenation device is provided with two sections of hydrogenation reactors; the reaction temperature of the first-stage hydrogenation reactor is 140-180 ℃, the reaction pressure is 7.5-8.5 MPa, the reaction temperature of the second-stage hydrogenation reactor is 180-250 ℃, and the reaction pressure is 13-14 MPa;
in the step 2, in the process of removing oxygen-containing impurities in the fast pyrolysis oil hydrogenation device, the liquid airspeed is 0.5h-1The biomass fuel consumption per cubic meter is 250-350 Nm3；
Step 3, converting the straight-run wax oil into refined wax oil through a wax oil hydrogenation device;
step 4, mixing refined wax oil and hydrogenated biomass oil to form a mixture, wherein the mass ratio of the refined wax oil is 80-95%, and the mass ratio of the hydrogenated biomass oil is 5-20%; the mixture is refined in a catalytic cracking device together, and meanwhile, catalytic diesel oil with biomass and catalytic gasoline with biomass are obtained; when the mixture is refined in a catalytic cracking device together, the reaction temperature is 490-520 ℃, and the reaction pressure is 0.1-0.2 MPa;
step 5, removing impurities from the catalytic diesel oil obtained in the step 4 in a catalytic diesel oil hydrogenation device, and performing hydrogenation upgrading to obtain a diesel oil product containing biomass; removing impurities from the catalytic gasoline obtained in the step (4) in a catalytic gasoline hydrogenation device, and performing hydrogenation upgrading to obtain a gasoline product containing biomass;
in the step 5, the reaction temperature of the catalytic diesel hydrogenation device is 290-340 ℃, the reaction pressure is 6-8 MPa, and the space velocity is 2-2.5 h-1；
In the step 5, the reaction temperature of the catalytic gasoline hydrogenation device is 240-300 ℃, the reaction pressure is 2-2.3 MPa, and the airspeed is 2.5-3 h-1。
2. The method for producing gasoline and diesel oil by co-refining fast pyrolysis biomass oil and straight-run wax oil according to claim 1, wherein in the step 1, woody biomass is pyrolyzed in a fast pyrolysis device; the pyrolysis reaction temperature is 500-550 ℃, and the pyrolysis time is 1.5-2.5 s.
3. The method for producing gasoline and diesel oil through co-refining of fast pyrolysis biomass oil and straight-run wax oil according to claim 1, wherein in the step 1, the yield of the obtained fast pyrolysis biomass oil is 50-60%, and the oxygen content in the biomass oil is 35-45%.
4. The method for producing gasoline and diesel oil through co-refining of fast pyrolysis biomass oil and straight-run wax oil according to claim 1, wherein in the step 2, the oxygen content of the prepared hydrogenated biomass oil is 15-25%.
5. The method for producing gasoline and diesel oil by co-refining the fast pyrolysis biomass oil and the straight-run wax oil according to any one of claims 1 to 4, wherein the oxygen content in the diesel oil containing biomass and the gasoline containing biomass prepared in the step 5 is less than or equal to 2.7 percent.
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| WO2011075671A2 (en) * | 2009-12-18 | 2011-06-23 | Growmark, Inc. | Oil recovery and syngas production from biomass-based processes |
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