CN116426313A - Method for producing light oil product by co-catalytic hydrogenation of lignin and heavy oil - Google Patents
Method for producing light oil product by co-catalytic hydrogenation of lignin and heavy oil Download PDFInfo
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- 239000003921 oil Substances 0.000 title claims abstract description 104
- 229920005610 lignin Polymers 0.000 title claims abstract description 97
- 239000000295 fuel oil Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 32
- 238000000197 pyrolysis Methods 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920005611 kraft lignin Polymers 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 42
- 229910052750 molybdenum Inorganic materials 0.000 description 21
- 239000011733 molybdenum Substances 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 10
- 235000018185 Betula X alpestris Nutrition 0.000 description 8
- 235000018212 Betula X uliginosa Nutrition 0.000 description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZBFFNPODXBJBPW-UHFFFAOYSA-N 1-hydroxy-1-phenylpropan-2-one Chemical group CC(=O)C(O)C1=CC=CC=C1 ZBFFNPODXBJBPW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
- C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of petrochemical industry and biomass resource utilization, and particularly relates to a method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil. Mixing lignin and heavy oil, and co-refining under the action of a hydrogenation catalyst to produce a light oil product; wherein the mass ratio of lignin to heavy oil is 1:100-30:100. The method improves the utilization rate of lignin raw materials; the liquid yield is high, and the product quality is good; processing of the inferior oil is completed while biomass is converted; the two raw material treatment processes have similar conditions, can share one set of device system, and has low investment cost.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry and biomass resource utilization, and particularly relates to a method for producing light oil products by co-catalytic hydrogenation of lignocellulose and heavy oil.
Background
Lignocellulose is the most abundant biomass resource on earth, and is mainly composed of three parts, namely cellulose (30-50% of dry matter weight), hemicellulose (20-40% of dry matter weight) and lignin (15-25% of dry matter weight), and is an important component of plant cell walls. Wherein, the cellulose and hemicellulose are polysaccharide composed of five-carbon sugar and six-carbon sugar monosaccharides; lignin is an amorphous aromatic polymer rich in oxo-phenylpropanol structures or structural units derived therefrom in molecular structures, and only lignin produced globally per year in the paper industry exceeds 5000 ten thousand tons.
At present, lignin conversion processes are numerous and mainly include acid/base catalyzed depolymerization, hydrolysis/pyrolysis, hydrogenation, oxidation, reforming, gasification and biodegradation (Chemical Reviews 115 (2015) 11559-11624.). The hydrogenation depolymerization method can directly convert lignin into liquid fuel with low oxygen content, has the advantages of good product selectivity, high heat value, coke formation inhibition in the process and the like, is suitable for industrial development, and is widely used in lignin conversion research and application.
Patent 201410539764.8 discloses a method for preparing bio-oil by lignin hydrogenation degradation, which comprises the steps of uniformly mixing lignin, a vanadium-based catalyst and a solvent, and preparing the bio-oil by hydrogenation catalytic degradation in a closed high-pressure reaction kettle; the mass ratio of the catalyst to the lignin is 1:10-100, and the volume ratio of the lignin to the solvent is 1:5-30; the reaction temperature is 150-400 ℃, the reaction time is 0.5-5 h, and the pressure of the reaction hydrogen is 0.5-6 MPa; the main component of the prepared biological oil is aromatic and phenolic compounds.
The patent 201510626276.5 discloses a method for converting lignin into liquid fuel by a one-step method, which comprises the steps of adding a lignin raw material, a composite solvent of a NaOH solution and a low-carbon alcohol solvent and a hydrogenation catalyst into a high-pressure reaction kettle, wherein the mass ratio of the lignin raw material to the NaOH solution to the low-carbon alcohol solvent is 2:45-75:1-4; the reaction is carried out for 3 to 7 hours under the conditions of 200 to 240 ℃ and 4 to 7MPa of pressure level and stirring at uniform speed, and the reaction products mainly comprise cyclohexanol and derivatives thereof.
201910437164.3A lignin catalytic depolymerization method is that lignin is added into a reaction vessel filled with solvent, and the lignin is degraded by the reaction under the synergistic effect of iron powder and palladium carbon; the mass volume dosage ratio of lignin to solvent is 20-25 mg/mL, the molar ratio of lignin to iron powder is 1:1-2, the mass ratio of lignin to palladium-carbon is 10:6-7, the reaction temperature is 80-160 ℃, and the reaction time is 4-12 h.
202011044296.9A method for preparing metal-acid-base function integrated catalyst and application of catalyst for preparing aromatic substance by breaking lignin ether bond by catalyzing lignin or lignin dimer in two-phase solvent of ethyl acetate/water with volume ratio of 4:1 with modified MgO site catalyst with amphiphilic interface; the reaction temperature is 140-220 ℃, the hydrogen pressure is 1.5-4 MPa, and the reaction time is 1-4 h.
As described above, the methods disclosed in the prior art all use a mixture of lignin and small organic molecule solvents (methanol, ethanol, tetrahydrofuran, etc.) as processing raw materials, and generally have problems of large addition amount of solvents and hydrogenation catalysts, low lignin liquefaction efficiency, and the like, so that large-scale conversion and industrial application of lignin raw materials are difficult to realize.
Disclosure of Invention
Aiming at the problems of complex components of wood raw materials, high oxygen content, difficult direct liquefaction, low product quality and the like, the invention provides a method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil.
In order to achieve the above purpose, the technical scheme adopted by the invention comprises the following steps:
a method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil, which is to mix lignin and heavy oil and co-refine the lignin and the heavy oil under the action of a hydrogenation catalyst to produce the light oil products; wherein the mass ratio of lignin to heavy oil is 1:100-30:100.
Further said
(1) Mixing lignin powder, heavy oil and a catalyst to obtain lignin slurry;
(2) Performing a co-catalytic hydrocracking process of wood (lignin) -oil (heavy oil) in a slurry bed reactor, and separating the obtained liquid product to obtain pyrolysis oil and solid residues;
(3) The pyrolysis oil is subjected to three processes of hydrogenation upgrading, hydrogenation refining and distillation separation in sequence to obtain light oil fractions (naphtha and diesel) and heavy oil fractions.
The heavy oil fraction is mixed with the heavy oil raw material and is recycled as the raw material for preparing lignin slurry oil.
The lignin is at least one of solvent lignin, alkaline lignin and Kraft lignin, and the particle size of lignin powder is less than 200 μm;
the heavy oil is at least one of heavy crude oil, normal pressure residual oil, vacuum residual oil, catalytic cracking slurry oil, hydrogenated cracking tail oil, deasphalted oil, coked heavy oil and shale oil.
The co-catalytic hydrocracking catalyst is a water-soluble or oil-soluble catalyst, wherein the active metal of the catalyst is at least one of Fe, co, mo, ni, W; the mass ratio of the active component of the catalyst to the heavy oil is 0.5:1000-4:1000.
The lignin slurry oil is prepared by mixing the lignin powder, heavy oil and a co-catalytic hydrocracking catalyst at 80-110 ℃, and then mixing the mixture, wherein the temperature of a slurry bed reactor is 350-450 ℃, the reaction pressure is 8-25 MPa, and the volume space velocity is 0.5-2 h -1 The volume ratio of the hydrogen to the oil is 600:1-1500:1, and the pyrolysis oil is separated and collected after the reaction.
The hydrocracking liquid phase product is solid particles such as catalyst, semicoke and the like after the reaction are removed through centrifugal separation;
the collected pyrolysis oil enters a first fixed bed reactor filled with a hydrogenation upgrading catalyst for hydrogenation upgrading, the reaction temperature is 320-430 ℃, the reaction pressure is 7-20 MPa, and the volume space velocity is 0.1-1 h -1 The volume ratio of the hydrogen oil is 600:1-1200:1, and the upgraded oil is obtained after the reaction.
The hydrogenation upgrading catalyst is a supported catalyst, and the used active metal is at least one of VIB and VIII metals; the carrier is at least one of alumina, silica and molecular sieve.
The upgraded oil enters a second fixed bed reactor filled with a hydrofining catalyst for hydrofining, and then is distilled and separated to obtain light oil fractions (naphtha and diesel) and heavy oil fractions; wherein, the hydrofining uses a fixed bed process, the reaction temperature is 300-400 ℃, the reaction pressure is 6-16 MPa, and the volume airspeed is 0.5-2 h -1 The volume ratio of the hydrogen to the oil is 400:1-1000:1.
The hydrofining catalyst is supported, and the used active metal is at least one of VIB and VIII metals; the carrier is at least one of alumina, silica and titania;
the distillation process is atmospheric distillation; the cutting temperature of the naphtha fraction is 60-180 ℃; the cutting temperature of the diesel oil fraction is 180-380 ℃.
The method provided by the invention has the following advantages:
the invention produces light oil by co-refining wood (lignin) -oil (heavy oil), wherein the process is that the two reactions of direct liquefaction of biotin and hydrocracking of heavy oil are organically combined; the heavy oil in the system is not only a reactant, but also can be used as a solvent to promote the dissolution of lignin at high temperature and high pressure, and simultaneously provides a place for storing and transferring hydrogen; meanwhile, the oxygen content of the raw material lignin is high, a certain amount of water can be generated in the system in the hydrogenation process, and the dissolution and removal of metal impurities in the heavy oil and the cracking of heavy oil molecules can be promoted at high temperature and high pressure. Further solves the problems of lower oil yield and easy coking of the device existing in the existing lignin processing process.
Detailed Description
The present invention will be further illustrated with reference to specific examples, but the present invention is not limited to the following embodiments.
Mixing lignin powder, heavy oil and a catalyst in proportion to obtain lignin slurry; (2) Performing lignin-heavy oil co-catalytic hydrocracking in a slurry bed reactor, and separating the obtained liquid product to obtain pyrolysis oil and solid residues; (3) The pyrolysis oil is subjected to three processes of hydrogenation upgrading, hydrogenation refining and distillation separation in sequence to obtain light oil fractions (naphtha and diesel) and heavy oil fractions; (4) The heavy oil fraction is mixed with the heavy oil raw material and recycled as the raw material for preparing lignin slurry oil.
The method improves the utilization rate of lignin raw materials; the liquid yield is high, and the product quality is good; processing of the inferior oil is completed while biomass is converted; the two raw material treatment processes are similar in condition, and can share one set of device system, so that the investment cost is low.
The following examples take the purchase of a sauter light oil vacuum residuum (see table 1) as an example for the production of light oils.
TABLE 1 vacuum residuum feedstock Properties
The lignin remembered in the examples below was obtained by extraction using birch bark as a raw material according to the patent (a method for extracting lignin from biomass, 201711392290.9).
Example 1
100g of lignin extracted from birch bark is fully mixed with 900g of Saint vacuum residuum preheated (the preheating temperature is 70-80 ℃ generally) (the properties of the vacuum residuum are shown in table 1), and then a mixture of nickel isooctanoate and molybdenum naphthenate is added as a catalyst to prepare lignin slurry oil. Wherein the total addition amount of active metal nickel and molybdenum in the catalyst is 0.05% of the total mass of the raw materials (the sum of lignin and heavy oil), and the atomic ratio of nickel to molybdenum is kept to be 1:1. Then, the prepared slurry oil was fed into a slurry bed reactor having a volume of 100mL by a feed pump, the reaction temperature was controlled at 410℃and the hydrogen pressure was 15MPa, the feed rate was 50g/h, and the hydrogen-oil ratio was 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 2 and 3.
Example 2
And (3) fully mixing 100g of lignin extracted from birch bark with 900g of preheated sauter vacuum residuum, and then adding a mixture of nickel isooctanoate and molybdenum naphthenate as a catalyst to prepare lignin slurry oil. Wherein, the total addition amount of the active metal nickel and molybdenum is 0.1 percent of the total mass of the raw materials, and the atomic ratio of the nickel to the molybdenum is kept to be 1:1. And then, the prepared slurry oil is input into a slurry bed reactor with the volume of 100mL by using a feed pump, the reaction temperature is controlled to be 410 ℃, the hydrogen pressure is controlled to be 15MPa, the feed amount is 50g/h, and the hydrogen-oil ratio is 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 2 and 3.
Example 3
And (3) fully mixing 100g of lignin extracted from birch bark with 900g of preheated sauter vacuum residuum, and then adding a mixture of nickel isooctanoate and molybdenum naphthenate as a catalyst to prepare lignin slurry oil. Wherein the total addition amount of the active metal nickel and molybdenum is 0.2% of the total mass of the raw materials, and the atomic ratio of nickel to molybdenum is kept to be 1:1. And then, the prepared slurry oil is input into a slurry bed reactor with the volume of 100mL by using a feed pump, the reaction temperature is controlled to be 410 ℃, the hydrogen pressure is controlled to be 15MPa, the feed amount is 50g/h, and the hydrogen-oil ratio is 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 2 and 3.
Example 4
And (3) fully mixing 100g of lignin extracted from birch bark with 900g of preheated sauter vacuum residuum, and then adding a mixture of nickel isooctanoate and molybdenum naphthenate as a catalyst to prepare lignin slurry oil. Wherein the total addition amount of the active metal nickel and molybdenum is 0.4% of the total mass of the raw materials, and the atomic ratio of nickel to molybdenum is kept to be 1:1. And then, the prepared slurry oil is input into a slurry bed reactor with the volume of 100mL by using a feed pump, the reaction temperature is controlled to be 410 ℃, the hydrogen pressure is controlled to be 15MPa, the feed amount is 50g/h, and the hydrogen-oil ratio is 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 2 and 3.
TABLE 2 elemental analysis results
| C/％ | H/％ | N/％ | S/％ | C/H | |
| Example 1 | 84.57 | 11.21 | 0.43 | 3.79 | 7.54 |
| Example 2 | 85.02 | 11.28 | 0.42 | 3.28 | 7.54 |
| Example 3 | 85.42 | 11.36 | 0.42 | 2.80 | 7.52 |
| Example 4 | 85.41 | 11.41 | 0.42 | 2.49 | 7.47 |
TABLE 3 four component analysis results
Example 5
And (3) fully mixing 50g of lignin extracted from birch bark with 950g of preheated sauter vacuum residuum, and then adding a mixture of nickel isooctanoate and molybdenum naphthenate as a catalyst to prepare lignin slurry. Wherein the total addition amount of active metal nickel and molybdenum is 0.4% of the total mass of the raw materials, and the atomic ratio of nickel to molybdenum is kept to be 1:1. And then, the prepared slurry oil is input into a slurry bed reactor with the volume of 100mL by using a feed pump, the reaction temperature is controlled to be 410 ℃, the hydrogen pressure is controlled to be 15MPa, the feed amount is 50g/h, and the hydrogen-oil ratio is 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 4 and 5.
Example 6
Fully mixing 150g of lignin extracted from birch bark with 850g of preheated sauter vacuum residuum, and then adding a mixture of nickel isooctanoate and molybdenum naphthenate as a catalyst to prepare lignin slurry oil. Wherein the total addition amount of the active metal nickel and molybdenum is 0.4% of the total mass of the raw materials, and the atomic ratio of nickel to molybdenum is kept to be 1:1. And then, the prepared slurry oil is input into a slurry bed reactor with the volume of 100mL by using a feed pump, the reaction temperature is controlled to be 410 ℃, the hydrogen pressure is controlled to be 15MPa, the feed amount is 50g/h, and the hydrogen-oil ratio is 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 4 and 5.
Example 7
And (3) fully mixing 200g of lignin extracted from birch bark with 800g of preheated sauter vacuum residuum, and then adding a mixture of nickel isooctanoate and molybdenum naphthenate as a catalyst to prepare lignin slurry oil. Wherein the total addition amount of the active metal nickel and molybdenum is 0.4% of the total mass of the raw materials, and the atomic ratio of nickel to molybdenum is kept to be 1:1. And then, the prepared slurry oil is input into a slurry bed reactor with the volume of 100mL by using a feed pump, the reaction temperature is controlled to be 410 ℃, the hydrogen pressure is controlled to be 15MPa, the feed amount is 50g/h, and the hydrogen-oil ratio is 1000:1. The obtained pyrolysis oil after the liquid-solid separation of the obtained product is subjected to element composition and four-component analysis, and specific data are shown in tables 4 and 5.
TABLE 4 elemental analysis results
| C/％ | H/％ | N/％ | S/％ | C/H | |
| Example 5 | 85.41 | 11.41 | 0.42 | 2.49 | 7.47 |
| Example 6 | 85.43 | 11.26 | 0.45 | 2.82 | 7.59 |
| Example 7 | 85.19 | 11.01 | 0.41 | 2.77 | 7.74 |
TABLE 5 four component analysis results
It can be seen from the above examples that blending lignin with heavy oil can achieve both high efficiency conversion of heavy oil and lignin.
Example 8
The pyrolysis oil obtained in example 4 was used as a raw material, and hydrogenation and upgrading were performed in a fixed bed reactor. The catalyst used was prepared with reference to the existing commercial hydrocracking catalyst, in which molybdenum trioxide contained 26wt%, nickel oxide contained 5wt%, silica contained 30wt%, alumina contained 39wt% and the specific surface area was 200m 2 /g, total pore volume 0.4mL/g. The reaction temperature is controlled to be 380 ℃, the reaction pressure is 15MPa, the hydrogen-oil ratio is 1000:1, and the liquid hourly space velocity is 0.3h -1 . The generated hydrogenation product is subjected to gas-liquid separation by a high-pressure separator, and then enters a reactor after hydrogen-rich gas is circulated, and the oil phase product is not subjected to fractionation for standby.
Example 9
Hydrogenation was carried out in a fixed bed reactor using the upgraded oil obtained in example 8 as a feedstockRefining. The catalyst used was prepared with reference to the existing commercial hydrofining catalyst, wherein molybdenum trioxide contained 13wt%, tungsten trioxide contained 11wt%, nickel oxide contained 3wt%, the balance being alumina carrier, the specific surface area was 140m 2 /g, total pore volume 0.7mL/g. The reaction temperature is controlled to be 360 ℃, the reaction pressure is 12MPa, the hydrogen-oil ratio is 800:1, and the liquid hourly space velocity is 1.0h -1 . The refined product is subjected to gas-liquid separation by a high-pressure separator, hydrogen-rich gas is circulated and enters a reactor, the oil phase product enters a fractionating tower for fractionation, and naphtha fraction and diesel fraction are obtained as light oil products for subsequent analysis, and specific data are shown in Table 6.
TABLE 6 Properties of different distillate products
As can be seen from the above Table 6, the lignin and the heavy oil are co-refined by the technical scheme of the invention to obtain a high-quality light oil product, thereby solving the problems of lower oil yield and easy coking of the device in the existing lignin processing process.
Claims (10)
1. A method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil is characterized in that lignin and heavy oil are mixed and co-refined under the action of a hydrogenation catalyst to produce light oil products; wherein the mass ratio of lignin to heavy oil is 1:100-30:100.
2. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 1, wherein the method comprises the steps of,
(1) Mixing lignin powder, heavy oil and a catalyst to obtain lignin slurry;
(2) Performing a co-catalytic hydrocracking process of wood (lignin) -oil (heavy oil) in a slurry bed reactor, and separating the obtained liquid product to obtain pyrolysis oil and solid residues;
(3) The pyrolysis oil is subjected to three processes of hydrogenation upgrading, hydrogenation refining and distillation separation in sequence to obtain light oil fractions (naphtha and diesel) and heavy oil fractions.
3. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 2, wherein the heavy oil fraction is mixed with heavy oil raw materials and recycled as raw materials for preparing lignin slurry oil.
4. The method for producing light oil by co-catalytic hydrogenation of lignin and heavy oil according to claim 1, wherein the lignin is at least one of solvent lignin, alkaline lignin and Kraft lignin, and the particle size of lignin powder is <200 μm;
the heavy oil is at least one of heavy crude oil, normal pressure residual oil, vacuum residual oil, catalytic cracking slurry oil, hydrocracking tail oil, deasphalted oil, coked heavy oil and shale oil.
5. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 2, wherein the co-catalytic hydrocracking catalyst is a water-soluble or oil-soluble catalyst, wherein the active metal of the catalyst is at least one of Fe, co, mo, ni, W; the mass ratio of the active component of the catalyst to the heavy oil is 0.5:1000-4:1000.
6. The method for producing light oil by co-catalytic hydrogenation of lignin and heavy oil according to claim 2 or 5, wherein the lignin slurry is prepared by mixing lignin powder, heavy oil and a co-catalytic hydrocracking catalyst at 80-110 ℃, and the temperature of a mixed slurry bed reactor is 350-450 ℃, the reaction pressure is 8-25 MPa and the volume space velocity is 0.5-2 h -1 The volume ratio of the hydrogen to the oil is 600:1-1500:1, and the pyrolysis oil is separated and collected after the reaction.
7. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 6,characterized in that the collected pyrolysis oil enters a first fixed bed reactor filled with a hydrogenation upgrading catalyst for hydrogenation upgrading, the reaction temperature is 320-430 ℃, the reaction pressure is 7-20 MPa, and the volume space velocity is 0.1-1 h -1 The volume ratio of the hydrogen oil is 600:1-1200:1, and the upgraded oil is obtained after the reaction.
8. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 7, wherein the hydrogenation upgrading catalyst is a supported catalyst, and the active metal used is at least one of group VIB and VIII metals; the carrier is at least one of alumina, silica and molecular sieve.
9. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 7, wherein the upgraded oil enters a second fixed bed reactor filled with a hydrofining catalyst for hydrofining, and then is distilled and separated to obtain light oil fractions (naphtha and diesel) and heavy oil fractions; wherein, the hydrofining uses a fixed bed process, the reaction temperature is 300-400 ℃, the reaction pressure is 6-16 MPa, and the volume airspeed is 0.5-2 h -1 The volume ratio of the hydrogen to the oil is 400:1-1000:1.
10. The method for producing light oil products by co-catalytic hydrogenation of lignin and heavy oil according to claim 9, wherein the hydrofining catalyst is a supported catalyst, and the active metal used is at least one of VIB and VIII metals; the carrier is at least one of alumina, silica and titania;
the distillation process is atmospheric distillation; the cutting temperature of the naphtha fraction is 60-180 ℃; the cutting temperature of the diesel oil fraction is 180-380 ℃.
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