CN109536197B

CN109536197B - Biomass liquefaction process

Info

Publication number: CN109536197B
Application number: CN201811457583.5A
Authority: CN
Inventors: 林科; 郭立新
Original assignee: Beijing SJ Environmental Protection and New Material Co Ltd
Current assignee: Beijing Haixin Energy Technology Co ltd
Priority date: 2018-11-30
Filing date: 2018-11-30
Publication date: 2020-10-16
Anticipated expiration: 2038-11-30
Also published as: CN109536197A

Abstract

The invention belongs to the technical field of biomass utilization, energy and chemical engineering, and particularly relates to a biomass liquefaction process. The liquefaction process adopts at least one of iron oxide, waste desulfurization agent of ferrite or regenerated product of waste desulfurization agent of iron oxide as catalyst, adopts aqueous slurry, and simultaneously controls the molar ratio of iron element and sulfur element in the reaction system, and finds that the carbonylation can be effectively utilized to block the free radical polycondensation of biomass in the cracking process in the presence of CO, and the conversion active hydrogen hydrogenation of CO and water can be realized.

Description

Biomass liquefaction process

Technical Field

The invention belongs to the technical field of biomass utilization, energy and chemical engineering, and particularly relates to a biomass liquefaction process.

Background

With the rapid development of social economy, stone non-renewable energy sources such as coal, crude oil, natural gas, oil shale and the like are gradually exhausted, and meanwhile, CO generated after the stone non-renewable energy sources are combusted₂、SO₂、NO_xThe environmental pollution caused by the pollutants is also becoming serious, which forces people to think about ways to obtain energy and methods to improve the environment.

At present, a biomass liquefaction technology becomes a new means for obtaining energy, the technology is an important component in biomass resource utilization, and the liquefaction mechanism is as follows: biomass is first cracked into oligomers, which are then dehydrated, dehydroxylated, dehydrogenated, deoxygenated and decarboxylated to form small molecule compounds, which are then reacted via condensation, cyclization, polymerization, etc. to produce new compounds. At present, the technology mainly comprises two main categories of indirect liquefaction and direct liquefaction, wherein the biomass direct liquefaction technology is to directly liquefy biomass from solid to liquid at proper temperature and pressure by adopting hydrolysis and supercritical liquefaction or introducing hydrogen and inert gas under the action of a solvent or a catalyst. In the whole process, pyrolysis liquefaction, catalytic liquefaction, pressurized hydrogenation liquefaction and the like are mainly involved.

In the biomass liquefaction process, before liquefaction, biomass raw materials are required to be dehydrated, so that the drying cost is increased, and even if the biomass raw materials are dried, a large amount of wastewater is generated after the whole process is finished. Moreover, the liquefaction process has strict requirements on reaction atmosphere and catalyst, and generally adopts pure hydrogen atmosphere and noble metal catalyst, so that the economy is poor. In addition, the calorific value of the oil product obtained by the liquefaction process is relatively low.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defects that the biomass raw material needs to be dehydrated, the reaction atmosphere and the catalyst have strict requirements, the calorific value of oil products is low and the generation amount of wastewater is large in the existing biomass liquefaction process, and further provide the biomass liquefaction process that the biomass raw material does not need to be dehydrated, the reaction atmosphere adopts an atmosphere containing CO, the calorific value of the oil products is high, the generation amount of wastewater is low and even no wastewater is generated.

Therefore, the technical scheme adopted by the invention for solving the problems is as follows:

the biomass liquefaction process provided by the invention comprises the following steps:

preparing slurry containing a catalyst and biomass, wherein the catalyst is a transition metal sulfide and/or oxide of a VIII group, and the slurry is aqueous slurry;

gasifying hydrocarbons and collecting CO-containing gas;

and mixing the slurry with pure CO or CO-containing gas for a liquefaction reaction, wherein the molar ratio of the iron element to the sulfur element in the reaction system is 1 (0.5-5), and thus obtaining the oil product.

Further, the gasification temperature is 350-;

the hydrocarbon is at least one of coal, mineral oil, coke, biomass, bio-renewable oil, natural gas, methane, biogas, methanol and ethanol;

adding a sulfur-containing compound into the catalyst until the molar ratio of the iron element to the sulfur element in the reaction system is 1 (0.5-5), preferably 1: (0.5-2), more preferably 1: (1-2).

Further, the temperature of the CO-containing gas is 250-600 ℃.

Further, the sulfur-containing compound is at least one of sulfur, hydrogen sulfide and carbon disulfide.

Further, the water in the aqueous slurry is derived from the water carried by the biomass, and the water content of the biomass is 500 ppm-20%, preferably 2% -10% based on the total weight of the biomass; or,

the water in the aqueous slurry is derived from externally added water.

Further, the CO content of the CO-containing gas is not less than 15% by volume, preferably not less than 25% by volume, most preferably not less than 50% by volume.

Further, the CO-containing gas is CO and H₂Or gasifying a product gas containing CO.

Further, the waste desulfurization agent of the ferrite compound is a waste desulfurization agent using iron oxide as an active component, and Fe_21.333O₃₂At least one of a waste desulfurizer which is an active component and a waste desulfurizer which takes FeOOH as an active component; or,

the regenerated product of the waste desulfurization agent of the ferrite compound is a regenerated product of a waste desulfurization agent taking iron oxide as an active component and takes Fe_21.333O₃₂At least one of a regenerated product of a spent devulcanizing agent which is an active component and FeOOH.

Further, the iron oxide is ferric oxide and/or ferroferric oxide.

Further, the ferric oxide is α -Fe₂O₃、α-Fe₂O₃.H₂O、γ-Fe₂O₃、γ-Fe₂O₃.H₂O, amorphous Fe₂O₃Amorphous Fe₂O₃.H₂At least one of O;

the ferroferric oxide is cubic ferroferric oxide;

the FeOOH is at least one of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, theta-FeOOH and amorphous FeOOH.

Further, the regenerated product of the spent desulfurization agent for ferrite compounds is a regenerated product obtained by oxidizing, sulfurizing and oxidizing the spent desulfurization agent for ferrite compounds by a slurry method.

Further, the regeneration method of the desulfurization waste agent of the ferrite compound comprises the following steps:

mixing the waste desulfurization agent of the iron oxide compound with water or an alkali solution to prepare slurry;

adding an oxidant into the slurry to perform primary oxidation reaction;

adding a vulcanizing agent into the slurry after the oxidation reaction to perform a vulcanization reaction;

adding an oxidant into the slurry after the vulcanization reaction to perform secondary oxidation reaction;

circularly carrying out the sulfuration reaction and the secondary oxidation reaction;

and carrying out solid-liquid separation on the slurry obtained after the secondary oxidation reaction to obtain a regenerated substance of the desulfurization waste agent of the iron oxide compound.

Further, the reaction pressure of the liquefaction reaction is 5-22MPa, and the reaction temperature is 200-470 ℃.

Further, the reaction time of the liquefaction reaction is not less than 15min, preferably 15-120 min.

Further, in the slurry, the content of the catalyst is 0.1-10 wt%;

the average particle size of the catalyst is 0.1 μm to 5mm, preferably 5 μm to 1000 μm, most preferably 5 to 200 μm.

Further, the slurry is mixed with pure CO or CO-containing gas for liquefaction reaction, and the method comprises the following steps:

and introducing CO-containing gas into the reaction system, and carrying out liquefaction reaction on the CO-containing gas and the slurry entering the reaction system.

Further, the volume ratio of the CO-containing gas to the slurry is (50-10000):1, preferably (100-: 1.

the pure CO or the gas containing CO is a gasified product, can be subjected to cooling, purification and transformation, then is pressurized and enters a reaction system, and can also directly enter the reaction system. Preferably, the liquefied gas is directly introduced into the liquefaction reaction system without pressure increase, purification and conversion.

Further, the reaction system is carried out in a reactor, and the reactor is any one of a suspension bed reactor, a slurry bed reactor, a bubbling bed reactor, a boiling bed reactor and a single-kettle reactor; or,

the reactor is one or more of a suspension bed reactor, a slurry bed reactor, a bubbling bed reactor, a boiling bed reactor and a single-kettle reactor which are connected in series or in parallel.

Further, the biomass solid is at least one of crop straws, wood, kitchen waste, excrement and animal carcasses.

Further, when the biomass is biomass solid, the preparation method of the slurry comprises the following steps: and sequentially carrying out primary crushing, compression and secondary crushing on the biomass, mixing the biomass with the catalyst to obtain a mixture, and adding the mixture into a solvent for pulping to obtain the slurry with the biomass content of 10-60 wt%.

Further, the bulk density of the biomass after the preliminary pulverization and the compression is not less than 0.4g/cm³Preferably not less than 0.8g/cm³More preferably not less than 1g/cm³。

The biomass after the secondary pulverization has an average particle size of not more than 5mm, preferably not more than 1mm, more preferably, an average particle size of not more than 500 μm, not more than 300 μm, not more than 60 μm, not more than 50 μm, not more than 5 μm, not more than 1 μm.

Further, the compression pressure is 0.5-3 MPa, and the temperature is 30-60 ℃.

Further, the solvent is water and/or oil.

Further, the oil content in the solvent is not less than 20% by weight, preferably not less than 50% by weight, and most preferably not less than 80% by weight;

further, the oil is one or more of animal and vegetable oil, mineral oil, distillate oil or the oil product.

The technical scheme of the invention has the following advantages:

1. the biomass liquefaction process provided by the invention adopts at least one of ferrite compounds, waste desulfurization agents of the ferrite compounds or regenerated products of the waste desulfurization agents of the iron oxide compounds as a catalyst, adopts aqueous slurry, and simultaneously controls the molar ratio of iron element to sulfur element in a reaction system, finds that the carbonylation can be effectively utilized to block the free radical polycondensation of biomass in the cracking process in the presence of CO, and realizes the purposeThe conversion active hydrogen of CO and water is hydrogenated, in the liquefaction reaction, the biomass does not need to be dehydrated, the liquefaction reaction can be directly carried out, the heat productivity of the prepared oil product can be improved while the liquefaction yield is improved, and a large amount of waste water can not be generated after the liquefaction reaction is finished. Meanwhile, CO-containing gas obtained after hydrocarbon gasification is directly adopted and is rich in CO and H₂、H₂S、CO₂Methane and the like at a temperature of 250-600 ℃, thereby not requiring gas purification, fully utilizing the high temperature and pressure of the gas containing CO, avoiding the energy consumption of the gas containing CO in cooling to normal temperature, and reducing the investment of cooling equipment, purifying equipment, gas boosting equipment and gas warming equipment.

2. The biomass liquefaction process provided by the invention further comprises the step of using the waste desulfurization agent of the ferrite compound as the waste desulfurization agent of a desulfurizer using iron oxide as an active component and using Fe_21.333O₃₂At least one of a waste desulfurizer which is an active component and a waste desulfurizer which takes FeOOH as an active component; the regenerated product of waste desulfurizing agent of ferrite compound is regenerated product of waste desulfurizing agent using iron oxide as active component, and uses Fe_21.333O₃₂The catalyst is used to be mixed with a proper amount of sulfur, and the catalyst is firstly combined with CO to form a carbonyl compound under the atmosphere of CO, then carbon atoms are grafted on small molecular active sites formed after thermal cracking of biomass (such as biomass) through the carbonyl compound, and meanwhile, the effects of CO transformation in-situ hydrogen production and catalytic hydrodeoxygenation are realized under the catalytic action of iron and sulfur elements, the oxygen content of oil products is reduced, and the liquefaction yield of solid biomass and the oil product yield of long molecular chain liquefaction to small molecules are greatly improved;

the regenerated material of spent desulfurization agent of ferrite compound is obtained by alternately subjecting ferrite compound to sulfidization and oxidative regeneration by a slurry method, and further, by a plurality of sulfidization-oxidation reactions, in the course of which iron oxide compound and iron sulfur compound crystal phase undergo reconstitution and liquefaction, plus S^2-Ionic radius (0.1)8nm) greater than O^2-Ionic radius (0.14nm), so with the liquefaction between Fe-O bond and Fe-S bond, the unit cell of the ferrite compound also undergoes contraction and expansion, and further causes the crystal particles of the iron oxide compound with stable structure to become loose and crack, and generates a large amount of nano iron compound which has good thiophilic property and is easy to be vulcanized. Meanwhile, the surface of the nano iron compound is covered with a non-polar elemental sulfur layer, the elemental sulfur layer can not only prevent the agglomeration and growth among the nano iron compound particles and greatly improve the dispersibility of the nano iron compound, but also can highly disperse the nano iron compound in a non-polar oil product by utilizing the similar compatibility characteristics existing among substances; moreover, the sulfur-covered nano iron compound can react with the nano iron compound at low temperature to generate pyrrhotite (Fe) with poor heavy oil hydrogenation activity because of the close sulfur-iron connection and the small particle size of the nano iron compound_1-xS), the regenerated product obtained by the method is small in particle size and good in lipophilicity, the structure of the regenerated product is a flaky nano structure, and the adsorbed sulfur is blocked between sheets, so that the agglomeration of the regenerated product is avoided, the adsorption capacity of CO is greatly improved, and the carbonylation, hydrogen production conversion and hydrogenation catalytic capacities are enhanced.

3. The biomass liquefaction process provided by the invention is characterized in that biomass solid is subjected to primary crushing, compression and secondary crushing in sequence, then is mixed with a catalyst to obtain a mixture, the mixture is added into a solvent to be ground and pulped to obtain the slurry with the biomass content of 10-60 wt% The conveying capacity of the body, thus improving the efficiency of the whole liquefaction process and reducing the industrial cost and energy consumption; in addition, the increase of the specific gravity of the biomass solid is also beneficial to the suspension and dispersion of the biomass solid in the slurry, so that the viscosity of the slurry can be reduced, the smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, the stable running and conveying of a pump are realized, and meanwhile, high-viscosity waste oil which cannot be used as a liquefaction solvent in the prior art, such as waste engine oil, illegal cooking oil, rancid oil and the like, can also be utilized.

4. The biomass liquefaction process provided by the invention regulates and controls the bulk density of the biomass which is subjected to primary crushing and compression to be not less than 0.4g/cm³Regulating and controlling the average particle size of the biomass subjected to secondary crushing to be less than 5mm, and adding the biomass into a solvent for grinding and pulping conveniently by the regulation and control mode, so that the solid content of the biomass in the slurry is improved;

the compression temperature is controlled to be 30-60 ℃, and the biomass is compressed at the temperature, so that the rheological property of biomass solids can be obviously enhanced, the viscosity of slurry is reduced, smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, and the stable running and conveying of a pump are realized.

5. According to the biomass liquefaction process provided by the invention, reaction raw materials and CO-containing gas are conveyed into a reactor, and reactions such as cracking, carbonylation, transformation, hydrogenation and the like are carried out in the reactor under the conditions of proper temperature, pressure, gas-liquid ratio and catalyst; further, by adopting a slurry bed reactor, firstly, reaction raw materials are fed into the slurry bed reactor from the bottom of the reactor to react, and simultaneously, gas containing CO is injected into the reactor, so that the difference control of the flow rate of each phase state can be realized in the reactor by depending on the different specific gravities of the gas, liquid and solid materials and matching with the change of the specific gravity difference caused by the yield of the light oil product after the reaction, the cracking, the carbonylation, the transformation, the hydrogenation and the reaction of the biomass solid raw materials are carried out in the reactor from bottom to top, even if the biomass solid with large specific gravity and the catalyst solid particles rise along with the gas and the light oil product in the process, the biomass solid and the catalyst solid particles return to the bottom to participate in the reaction again under the action of the gas containing CO at the upper part, and the injection quantity of the gas containing CO in the slurry entering the reactor are properly adjusted according to the material densities at the upper part, thereby realizing the circulation of the unliquefied biomass in the reactor and the balanced discharge of the catalyst, ensuring the full progress of various reactions, and being beneficial to improving the liquefaction rate and the bio-oil yield of the biomass

6. According to the biomass liquefaction process provided by the invention, the biomass does not need to be dehydrated, so that the drying cost is reduced; the gas containing CO is used in the reaction process, the gas containing CO can be pure CO or impure, for example, the gas contains CO, hydrogen sulfide, methane and the like, and can also be synthesis gas generated by gasifying coal, biomass, natural gas and mineral oil, the rest gas except CO in the synthesis gas can be a mixture containing hydrogen, carbon dioxide or methane and ethane, and the gas manufacturing cost is greatly reduced; in the reaction process, the combined processes of cracking reaction, carbonylation reaction, shift reaction, hydrogenation reaction and the like are realized by using gas containing CO and adopting the action of an iron-based catalyst or a waste agent with low price, sufficient free radicals are easily provided, carbonization and coking of biomass are avoided, the conversion rate of the biomass and the liquid yield are high, and the reaction temperature and the pressure are reduced; the oil produced by the liquefaction process can also be used in a preceding process to prepare a slurry.

Detailed Description

The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The embodiment provides a biomass liquefaction process, which comprises the following steps:

pretreatment of biomass:

rice straw and reed straw are used as biomass solid, the water content of the biomass is 4% based on the total weight of the biomass, and the rice straw and the reed straw are sent into superfine powderPrimarily crushing by a crusher, wherein the median particle size after primary crushing is 100 mu m, then feeding the primarily crushed rice straws and reed straws into a briquetting machine, compressing at the temperature of 30 ℃ and under the pressure of 3MPa, and carrying out extrusion molding until the bulk density is 0.8g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;

catalyst:

the catalyst is a waste agent of the desulfurizer taking FeOOH as an active component, wherein soluble iron salt Fe (NO) is contained in the desulfurizer taking FeOOH as the active component₃)₃·9H₂6g of O, 9g of ferric salt complexing agent triethanolamine and 15g of amorphous iron oxyhydroxide;

the desulfurizer using FeOOH as the active component is used for removing H in waste gas₂The process of S is as follows: h is to be₂The S content is 5500mg/cm³Is used for 3000h^-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section₂When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste agent of the desulfurizer which takes FeOOH as an active component in the embodiment;

adding sulfur: detecting the molar ratio of the iron element to the sulfur element in the waste desulfurizer using FeOOH as an active component in the embodiment, and if the molar ratio of the iron element to the sulfur element does not reach 1:5, doping solid sulfur powder into the catalyst until the molar ratio of the iron element to the sulfur element is 1:5, thereby ensuring that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 5;

if the molar ratio of the iron element to the sulfur element is more than 1:5, redundant sulfur can be removed by solvent extraction or heating sulfur melting and other modes;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into hogwash oil, stirring and grinding the mixture to prepare slurry, and detecting that the total content of rice straws and reed straws in the slurry is 60 wt%, the viscosity of the slurry is 500mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 5 wt%, and the average particle size of the added catalyst is 5 mu m;

CO-containing gas:

carrying out high-temperature and high-pressure gasification on rice straws and reed straws at 800 ℃ and 15MPa, and collecting CO-containing gas at the temperature of 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (CO is 40% and H)₂Accounting for 20 percent) is directly injected into the slurry bed reactor from the inlet of the slurry bed reactor, and the slurry enters the slurry bed reactor to carry out cracking, carbonylation, transformation and hydrogenation reactions, the reaction pressure of the liquefaction reaction is controlled to be 20MPa, the reaction temperature is 380 ℃, the reaction time is 60min, and the volume ratio of the CO-containing gas to the slurry is 3000: 1, preparing an oil product.

Example 2

pretreatment of biomass:

wheat straw and corn straw are used as biomass solid, the water content of the biomass is 10% based on the total weight of the biomass, the wheat straw and the corn straw are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 300 mu m, then the wheat straw and the corn straw after primary pulverization are sent into a briquetting machine for compression and extrusion molding at the temperature of 60 ℃ and the pressure of 0.5MPa until the bulk density is 0.9g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 5mm for later use;

catalyst:

the catalyst is a waste agent of a desulfurizer taking iron oxide as an active component, wherein in the desulfurizer taking iron oxide as the active component, 10g of calcium bicarbonate, 12g of basic copper carbonate and gamma-Fe₂O₃18g，MnO₂8g of NiO and 5g of NiO;

the desulfurization process of the desulfurizing agent with iron oxide as the active component is summarized as follows:

1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;

2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;

3) the tail gas is treated for 2000h^-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer which takes iron oxide as an active component is obtained;

adding sulfur: detecting the molar ratio of the iron element to the sulfur element in the waste desulfurizer using the iron oxide as the active component in the embodiment, and if the molar ratio of the iron element to the sulfur element does not reach 1:1, adding solid sulfur powder into the catalyst until the molar ratio of the iron element to the sulfur element is 1:1, thereby ensuring that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 1;

if the molar ratio of the iron element to the sulfur element is more than 1:1, redundant sulfur can be removed by conventional ways such as solvent extraction or heating for sulfur melting;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into palm oil, stirring and dispersing for pulping to form a slurry, wherein the total content of wheat straws and corn straws in the slurry is 50 wt%, the viscosity of the slurry is 1400mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 1 wt%, and the average particle size of the added catalyst is 10 mu m;

CO-containing gas:

gasifying residual oil in petroleum at 1200 ℃ and 8MPa, and collecting CO-containing gas at the temperature of 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (35% of CO and H)₂The proportion is 37%) is injected into the suspension bed reactor from a suspension bed reaction inlet, and the slurry entering the suspension bed reactor undergoes cracking, carbonylation, transformation and hydrogenation reactions, the reaction pressure of the liquefaction reaction is controlled to be 15MPa, the reaction temperature is controlled to be 420 ℃, and the reaction time is controlled to be30min, the volume ratio of the CO-containing gas to the slurry being 2000: 1, preparing an oil product.

Example 3

pretreatment of biomass:

the method comprises the steps of taking cotton straws as biomass solid, enabling the water content of the biomass to be 1% based on the total weight of the biomass, sending the cotton straws into a superfine pulverizer to be primarily pulverized, enabling the median particle size after primary pulverization to be 200 mu m, then sending the primarily pulverized cotton straws into a plodder to be compressed and extruded and molded at the temperature of 40 ℃ and under the pressure of 2MPa until the bulk density of the cotton straws is 0.9g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 1mm for later use;

catalyst:

the catalyst is amorphous FeOOH; adding sulfur: adding solid sulfur powder into the catalyst until the molar ratio of the iron element to the sulfur element is 1:2, so as to ensure that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 2;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into petroleum-based wax oil to disperse and pulp to form slurry, and detecting that the total content of cotton straws in the slurry is 50 wt%, the viscosity of the slurry is 400mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 1 wt%, and the average particle size of the added catalyst is 10 microns;

CO-containing gas:

gasifying the straw particles at the high temperature of 900 ℃ and under the pressure of 5MPa, and collecting CO-containing gas at the temperature of 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (CO 50% and H)₂20 percent of the total content of the components) is injected into the boiling bed reactor from an inlet of the boiling bed reactor, and the boiling bed reactor and the slurry entering the boiling bed reactor undergo cracking, carbonylation, transformation and hydrogenation reactions, and the reaction pressure of the liquefaction reaction is controlled to be 16 percentMPa, the reaction temperature is 440 ℃, the reaction time is 40min, and the volume ratio of the CO-containing gas to the slurry is 1000: 1, preparing an oil product.

Example 4

pretreatment of biomass:

wood chips and soybean straws are used as biomass solid, the water content of the biomass is 2% based on the total weight of the biomass, the wood chips and the soybean straws are fed into a superfine pulverizer to be primarily pulverized, the median particle size after primary pulverization is 150 mu m, and then the wood chips and the soybean straws after primary pulverization are fed into a briquetting machine to be compressed and extruded and molded at the temperature of 50 ℃ and under the pressure of 1MPa until the bulk density is 1g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 4mm for later use;

catalyst:

the catalyst is a regeneration product of a waste agent of a desulfurizer taking ferric oxide as an active component, wherein in the desulfurizer taking ferric oxide as the active component, 50g of cubic system ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose are contained;

the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:

(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;

(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer containing iron oxide in the application;

the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:

1) stirring the waste agent and water in a slurry tank to prepare slurry, wherein the solid content of the slurry is 12 wt%;

2) introducing sodium hypochlorite into the slurry, and carrying out oxidation reaction at 60 ℃ and 1MPa to carry out oxidation regeneration;

3) adding Na into the oxidized slurry₂S, carrying out a vulcanization reaction at 10 ℃ and 5 MPa;

4) introducing hydrogen peroxide into the vulcanized slurry, and carrying out oxidation reaction at 30 ℃ and 1.1MPa to carry out oxidation regeneration;

5) repeating the steps 3) and 4) once to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 1.8;

6) carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent;

adding sulfur: adding solid sulfur powder into the regenerated substances until the molar ratio of the iron element to the sulfur element is 1:2, so as to ensure that the molar ratio of the iron element to the sulfur element in a reaction system is 1: 2;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into rapeseed oil, shearing and pulping to form slurry, wherein the total content of wood chips and soybean straws in the slurry is 40 wt%, the viscosity of the slurry is 1000mPa ∙ s (50 ℃), the content of regenerants of the waste desulfurizer using iron oxide as an active component in the slurry is 2 wt%, and the average particle size of the added regenerants of the waste desulfurizer using iron oxide as an active component is 400 mu m;

CO-containing gas:

gasifying the illegal cooking oil at 1100 ℃ and 19Mpa under high temperature and high pressure, and collecting CO-containing gas at the temperature of 250-600 ℃;

and (3) liquefaction reaction:

injecting CO-containing gas (wherein the volume ratio of CO is 40%) into the bubbling bed reactor from 4 injection ports on the side wall and the bottom of the bubbling bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the bubbling bed reactor, controlling the reaction pressure of liquefaction reaction to be 18MPa, the reaction temperature to be 380 ℃, and the reaction time to be 100min, wherein the volume ratio of the CO-containing gas to the slurry is 950: 1, preparing an oil product.

Example 5

pretreatment of biomass:

pea straw, sorghum straw and rice straw are used as biomass solid, the water content of the biomass is 15% based on the total weight of the biomass, the pea straw, the sorghum straw and the rice straw are sent into an ultrafine grinder to be primarily ground, the median particle size after primary grinding is 250 mu m, and then the primarily ground pea straw, sorghum straw and rice straw are sent into a plodder to be compressed and extruded and formed at the temperature of 55 ℃ and under the pressure of 1.5MPa until the bulk density is 0.9g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 0.9mm for later use;

catalyst:

the catalyst is Fe_21.333O₃₂A regenerated product of a spent agent of a desulfurizing agent as an active component, wherein the Fe is used_21.333O₃₂Among desulfurizing agents as active components, Fe_21.333O₃₂Is 55g of anatase type Ti0₂22g of bentonite, 15g of bentonite;

above with Fe_21.333O₃₂The desulfurization process of the desulfurizer which is an active component comprises the following operation steps:

the catalyst is filled in a fixed bed reactor to contain H₂And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h^-1The waste catalyst after gas field water desulfurization is Fe_21.333O₃₂A waste agent of a desulfurizing agent which is an active component;

the regeneration method of the waste agent comprises the following steps:

1) dispersing the waste agent in water to form slurry;

2) heating the slurry to 45 ℃ at normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, introducing air, controlling the flow rate of the hydrogen peroxide to be 500mL/min and the air flow to be 100mL/min, and magnetically stirring to promote the reaction for 5 min;

3) after the reaction is finished, filtering reaction liquid, washing the obtained precipitate for 3 times by using water, and naturally drying to obtain a regenerated substance of the waste agent;

adding sulfur: adding solid sulfur powder into the regenerated substance until the molar ratio of the iron element to the sulfur element is 1:4, so as to ensure that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 4;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into mixed oil of illegal cooking oil and rapeseed oil for homogenizing and pulping to form slurry, wherein the illegal cooking oil and the rapeseed oil adopted in the subsequent slurry preparation process can be replaced by oil products prepared by the biomass liquefaction process in the embodiment, through detection, the total content of pea straws, sorghum straws and rice straws in the slurry is 40 wt%, the viscosity of the slurry is 820mPa ∙ s (50 ℃), and Fe is used as Fe in the slurry_21.333O₃₂The content of the regenerant of the waste desulfurizer as an active component is 8 wt%, and the added Fe_21.333O₃₂The average particle diameter of the regenerant of the spent desulfurizer as an active component is 300 μm;

CO-containing gas:

gasifying pulverized coal at 1600 ℃ and 8MPa, and collecting CO-containing gas at 250-600 ℃;

and (3) liquefaction reaction:

injecting CO-containing gas (wherein the volume ratio of CO is 47%) into the slurry bed reactor from 5 injection ports on the bottom and the side wall of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the slurry bed reactor, controlling the reaction pressure to be 17MPa, the reaction temperature to be 400 ℃, the reaction time to be 50min, and controlling the volume ratio of the CO-containing gas to the slurry to be 1500: 1, preparing an oil product.

Example 6

pretreatment of biomass:

wheat straw and flax straw are used as biomass solid, the water content of the biomass is 9% based on the total weight of the biomass, the wheat straw and the flax straw are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 300 mu m, then the wheat straw and the flax straw after primary pulverization are sent into a plodder for compression at the temperature of 60 ℃ and under the pressure of 3MPa, and the compression molding is carried out until the bulk density is 1.1g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 2mm for later use;

catalyst:

the catalyst is a regeneration of a waste desulfurizer of which the FeOOH is taken as an active component, wherein the total mass of the desulfurizer of which the FeOOH is taken as the active component is 30g, the amorphous FeOOH is 20g, the potassium oxide is 8g, and the adhesive kaolin is 10 g;

the desulfurization process of the tail gas generated after the desulfurization agent with the FeOOH as the active component is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:

3) the tail gas is treated for 2000h^-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer with the active component is obtained;

the regeneration method of the waste agent comprises the following steps:

1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;

2) introducing air into the slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;

3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;

4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;

5) repeating the steps 3) and 4) once to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 2;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into mixed oil of palm oil and petroleum-based wax oil, and stirring and pulping to form slurry; through detection, the total content of wheat straws and flax straws in the slurry is 45 wt%, the viscosity of the slurry is 530mPa ∙ s (50 ℃), the content of the regenerant of the waste desulfurizer taking the iron oxyhydroxide as the active component in the slurry is 0.3 wt%, and the average particle size of the added regenerant of the waste desulfurizer taking the iron oxyhydroxide as the active component is 20 micrometers;

adding sulfur: adding solid sulfur powder into the regenerated substances until the molar ratio of the iron element to the sulfur element is 1:2.5, so as to ensure that the molar ratio of the iron element to the sulfur element in a reaction system is 1: 2.5;

CO-containing gas:

gasifying the sunflower stem particles at 900 ℃ and 3MPa, and collecting CO-containing gas at the temperature of 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (CO 60% and H)₂The percentage is 10%) is injected into the slurry bed reactor from 3 injection ports on the bottom and the side wall of the slurry bed reactor, and the slurry entering the slurry bed reactor undergoes cracking, carbonylation, transformation and hydrogenation reactions, the reaction pressure is controlled to be 19MPa, the reaction temperature is controlled to be 420 ℃, the reaction time is 100min, and the volume ratio of the CO-containing gas to the slurry is 800: 1, preparing an oil product.

Example 7

pretreatment of biomass:

taking rice straws and broad bean straws as biomass solids, taking the total weight of the biomass as the water content of the biomass, feeding the rice straws and the broad bean straws into a superfine pulverizer for primary pulverization, wherein the median particle size after the primary pulverization is 100 mu m, then feeding the rice straws and the broad bean straws after the primary pulverization into a briquetting machine for compression at the temperature of 30 ℃ and under the pressure of 0.5MPa, and carrying out extrusion molding until the bulk density is 1.0g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 1mm for later use;

catalyst:

the catalyst is a regeneration product of a waste agent of a desulfurizer taking ferric oxide as an active component, wherein in the desulfurizer taking ferric oxide as the active component, 12g of cubic system ferroferric oxide and amorphous Fe₂O₃24g of amorphous Fe₂O₃.H₂O39 g and NiO are 5 g;

the desulfurizer removes H in the waste gas₂The matrix process of S comprises the following steps: h is to be₂The S content is 5500mg/cm³Is used for 3000h^-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section₂When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section;

the method for regenerating the waste agent of the desulfurizer by using the ferric oxide as the active component comprises the following steps:

the regeneration method of the waste agent comprises the following steps:

1) washing the waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain particles of 200 meshes to obtain waste agent powder;

2) preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;

3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, introducing air, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste agent;

adding sulfur: adding solid sulfur powder into the regenerated substances until the molar ratio of the iron element to the sulfur element is 1:0.9, so as to ensure that the molar ratio of the iron element to the sulfur element in a reaction system is 1: 0.9;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into coal tar to disperse and pulp to form slurry, wherein the total content of rice straws and broad bean straws in the slurry is 55 wt%, the viscosity of the slurry is 510mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 0.2 wt%, and the average particle size of the added catalyst is 2 mu m;

CO-containing gas:

gasifying coal at 1400 ℃ and 5MPa, and collecting CO-containing gas at 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (CO accounting for 45% and H)₂The ratio is 22%) is injected into the slurry bed reactor from 3 injection ports on the side wall of the slurry bed reactor, and the slurry entering the slurry bed reactor undergoes cracking, carbonylation, transformation and hydrogenation reactions, the reaction pressure is controlled to be 20MPa, the reaction temperature is 410 ℃, the reaction time is 110min, and the volume ratio of the CO-containing gas to the slurry is 650: 1, preparing an oil product.

Example 8

pretreatment of biomass:

corn stalks and ramie stalks are taken as biomass solids, the water content of the biomass is 20 percent based on the total weight of the biomass, the corn stalks and the ramie stalks are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 300 mu m, and then the corn stalks and the ramie stalks after primary pulverization are sent into a briquetting machine for compression and extrusion molding at the temperature of 50 ℃ and the pressure of 2.5MPa until the bulk density is 0.8g/cm³Then proceed to twoPerforming secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;

catalyst:

the catalyst is a waste agent of the desulfurizer taking FeOOH as an active component, wherein, in the desulfurizer taking FeOOH as the active component, 70g of amorphous FeOOH and 70g of Co₂O₃25g and NiO is 5 g;

the desulfurizer which takes FeOOH as the active component removes H in the waste gas₂The basic process of S comprises the following steps: h is to be₂The S content is 5500mg/cm³Is used for 3000h^-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section₂When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste agent of the desulfurizer which takes FeOOH as an active component in the embodiment;

adding sulfur: adding solid sulfur powder into the waste agent until the molar ratio of the iron element to the sulfur element is 1:3, so as to ensure that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 3;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into swill-cooked dirty oil for emulsification pulping to form slurry, wherein the total content of corn straws and ramie straws in the slurry is 57 wt%, the viscosity of the slurry is 1130mPa ∙ s (50 ℃), the content of the waste agent of the desulfurizer taking FeOOH as an active component in the slurry is 4 wt%, and the average particle size of the added waste agent of the desulfurizer taking FeOOH as the active component is 120 mu m;

CO-containing gas:

gasifying petroleum wax oil at the high temperature of 1100 ℃ and under the pressure of 16MPa, and collecting CO-containing gas at the temperature of 250-600 ℃;

and (3) liquefaction reaction:

injecting CO-containing gas into the slurry bed reactor from 4 injection ports on the bottom and the side wall of the slurry bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reaction on the CO-containing gas and the slurry entering the slurry bed reactor, wherein the reaction pressure is controlled to be 17MPa, the reaction temperature is controlled to be 400 ℃, the reaction time is 40min, and the volume ratio of the CO-containing gas to the slurry is 950: 1, preparing an oil product.

Example 9

pretreatment of biomass:

catalyst:

the catalyst adopts a waste desulfurizer which takes FeOOH as an active component, wherein the content of amorphous FeOOH in the desulfurizer which takes FeOOH as the active component is 60%, the content of carrier diatomite is 30%, and the content of binder cellulose powder is 10%;

adding sulfur: adding solid sulfur powder into the catalyst until the molar ratio of the iron element to the sulfur element is 1:4, so as to ensure that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 4;

preparing biomass slurry:

mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into mixed oil of illegal cooking oil and rapeseed oil for homogenizing and pulping to form slurry, wherein the illegal cooking oil and the rapeseed oil adopted in the subsequent slurry preparation process can be replaced by oil products prepared by the biomass liquefaction process in the embodiment, through detection, the total content of pea straws, sorghum straws and rice straws in the slurry is 40 wt%, the viscosity of the slurry is 820mPa ∙ s (50 ℃), the content of a desulfurizer taking FeOOH as an active component in the slurry is 8 wt%, and the average particle size of the added desulfurizer taking FeOOH as the active component is 300 mu m;

CO-containing gas:

gasifying the sorghum straw powder at a high temperature of 900 ℃, and collecting CO-containing gas at a temperature of 250-600 ℃;

and (3) liquefaction reaction:

injecting CO-containing gas (wherein the volume ratio of CO is 40%) into the slurry bed reactor from 5 injection ports on the bottom and the side wall of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the slurry bed reactor, controlling the reaction pressure to be 17MPa, the reaction temperature to be 380 ℃, and the reaction time to be 50min, wherein the volume ratio of the CO-containing gas to the slurry bed reactor is 900: 1, preparing an oil product.

Example 10

The embodiment provides a liquefaction process of oil residue and excrement, which comprises the following steps:

pretreatment of oil residue and excrement:

oil residue and feces are used as biomass solid, the water content of the biomass is 12% based on the total weight of the biomass, the oil residue and the feces are sent into an ultrafine pulverizer for primary pulverization, the median particle size after primary pulverization is 150 mu m, then the oil residue and the feces after primary pulverization are sent into a plodder for compression at the temperature of 55 ℃ and under the pressure of 1.5MPa, and extrusion molding is carried out until the bulk density is 1.0g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 2mm for later use;

catalyst:

the catalyst is amorphous FeOOH;

adding sulfur: adding solid sulfur powder into the catalyst until the molar ratio of the iron element to the sulfur element is 1:1.5, so as to ensure that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 1.5;

preparing slurry:

mixing the oil residue and the feces obtained by pretreatment with the catalyst to obtain a mixture, adding the mixture into petroleum-based wax oil to be dispersed and pulped to form slurry, detecting that the total content of the oil residue and the feces in the slurry is 50 wt%, the viscosity of the slurry is 400mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 1 wt%, and the average particle size of the added catalyst is 10 microns;

CO-containing gas:

gasifying coal at 1350 ℃ and 6MPa, and collecting CO-containing gas at 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (CO accounting for 45% and H)₂25%) is injected into the fluidized bed reactor from the inlet of the fluidized bed reactor, and the slurry entering the fluidized bed reactor is subjected to cracking, carbonylation, transformation and hydrogenation reactions, the reaction pressure of the liquefaction reaction is controlled to be 16MPa, the reaction temperature is 420 ℃, the reaction time is 40min, and the volume ratio of the CO-containing gas to the slurry is 1000: 1, preparing an oil product.

Example 11

The embodiment provides a co-liquefaction process of oil residue and wheat straw, which comprises the following steps:

pretreatment of oil residue and wheat straw:

oil residue and wheat straw are taken as biomass solid, the water content of the biomass is 5% based on the total weight of the biomass, the oil residue and the excrement are sent into an ultrafine grinder for primary grinding, the median particle size after primary grinding is 200 mu m, then the oil residue and the excrement after primary grinding are sent into a plodder for compression at the temperature of 55 ℃ and under the pressure of 1.5MPa, and extrusion forming is carried out until the bulk density is 0.95g/cm³Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 60 mu m for later use;

catalyst:

the catalyst is a regenerated product of waste desulfurizer containing FeOOH, wherein the content of gamma-FeOOH in the FeOOH-containing desulfurizer is 45%, the content of alpha-FeOOH is 35%, the content of carrier molecular sieve is 15%, and the content of binder sesbania powder is 5% by total mass of the FeOOH-containing desulfurizer;

the catalyst removes H in the exhaust gas₂The basic process of S comprises the following steps: h is to be₂The S content is 5500mg/cm³Is used for 3000h^-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section₂When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the desulfurizer waste agent;

the regeneration method of the waste desulfurizer comprises the following steps: washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into 80-mesh particles to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, sampling and inspecting after reacting for a period of time, and when the sample taken out is reacted with hydrochloric acid, H is not generated₂S, completely liquefying iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, and using CC1 to obtain the solid material₄And (3) extracting the solid material obtained after the extraction and filtration for three times, combining the extraction liquid, recovering the solvent by using a distillation method, simultaneously obtaining the crystallized elemental sulfur, and mixing the residual solid after the extraction liquid is separated with adhesive sesbania powder to obtain the regenerated product of the desulfurizer waste agent, wherein the using amount of the adhesive sesbania powder is 5% of the mass of the solid.

Adding carbon disulfide: adding carbon disulfide into the catalyst until the molar ratio of the iron element to the sulfur element is 1:2, so as to ensure that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 2;

preparing slurry:

mixing the pretreated oil residue and wheat straws with the catalyst to obtain a mixture, adding the mixture into illegal cooking oil for dispersing and pulping to form slurry, wherein the total content of the oil residue and the excrement in the slurry is 55 wt%, the viscosity of the slurry is 400mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 10 wt%, and the average particle size of the added catalyst is 5 mm;

CO-containing gas:

gasifying the hogwash oil at 1050 ℃ and 6MPa, and collecting CO-containing gas at 250-600 ℃;

and (3) liquefaction reaction:

mixing CO-containing gas (35% of CO and H)₂The ratio is 24%) is injected into the fluidized bed reactor from an inlet of the fluidized bed reactor, and the slurry entering the fluidized bed reactor is subjected to cracking, carbonylation, transformation and hydrogenation reactions, the reaction pressure of the liquefaction reaction is controlled to be 16MPa, the reaction temperature is 360 ℃, the reaction time is 60min, and the volume ratio of the CO-containing gas to the slurry is 5000: 1, preparing an oil product.

Example 12

The embodiment provides a biomass liquefaction process, which is the same as the embodiment 4, and the only difference is that the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:

1) introducing water vapor with the pressure of 1.5MPa into a heating furnace, and heating the water vapor to 450 ℃;

2) introducing the heated water vapor into a desulfurization tank containing the waste agent at the speed of 15m/s, and heating the waste agent;

3) ensuring that the bed layer temperature of the waste agent is heated to above 400 ℃ by water vapor and runs for 2 hours, wherein the steam consumption is 6 t/h;

4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;

5) introducing coke oven gas subjected to primary hydrogenation in the fine desulfurization process to reduce the iron oxide desulfurizer waste agent at 800m 3/h;

6) analyzing the concentration change of the inlet and outlet H2 every 30min after introducing the coke oven gas, and obtaining the regeneration after the concentration of the outlet H2 is stably more than or equal to the concentration of the inlet H2 (3 times of analysis).

Comparative example 1

This comparative example provides a biomass liquefaction process, which is the same as example 4, except that: in the comparative example, the wood chips and the soybean straws are taken as biomass solids, and the water content of the biomass is 80ppm based on the total weight of the biomass; the molar ratio of the iron element to the sulfur element in the reaction system is 1: 0.1.

Test example 1

The distribution of the products prepared using the processes of examples 1-12 of the present invention was compared to comparative example 1 and the products were tested as follows:

the liquefaction ratio of solid biomass = (total mass of solid biomass in raw material-mass of solid biomass remaining in reaction product)/total mass of solid biomass in raw material, and "solid biomass" in the liquefaction ratio of solid biomass refers to anhydrous and ashless groups (the same applies hereinafter);

the yield of the solid biomass liquefied oil is equal to the mass of the liquid phase oil product in the product obtained by liquefying the solid biomass at normal temperature and normal pressure/the total feeding mass of the solid biomass in the raw material;

the reaction water yield = (mass of water of reaction product-total mass of water initially added in the reaction or carried in by raw material)/total mass of raw material fed. When this value is < 0, it is marked as "none";

the corresponding test results are shown in tables 1 and 2:

table 1 comparison of liquefaction effect of solid biomass

As can be seen from the data in table 1, the catalyst performs the functions of hydrothermal conversion, deoxidation, hydrogenation and cracking under the high-temperature and high-pressure reaction conditions of the CO-containing gas produced by the gasification process, so that the biomass solids are fully converted into the biomass fuel, and no excess water is generated; in the comparative example, the conversion rate of biomass was low due to the low water content in the slurry and the low sulfur content in the catalyst.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. A biomass liquefaction process, characterized by comprising the steps of:

preparing a slurry containing a catalyst and biomass, wherein the catalyst is at least one of ferrite compounds, desulfurization waste agents of the ferrite compounds or regeneration products of the desulfurization waste agents of the iron oxide compounds, and the slurry is aqueous slurry;

gasifying hydrocarbons and collecting CO-containing gas; the gasification temperature is 350-1600 ℃, and the pressure is 1-20 MPa;

mixing the slurry with a CO-containing gas for a liquefaction reaction, wherein the molar ratio of the iron element to the sulfur element in the reaction system is 1 (0.5-5), and preparing an oil product; the CO-containing gas is directly subjected to liquefaction reaction without pressure rise, purification and transformation;

the reaction pressure of the liquefaction reaction is 5-22MPa, and the reaction temperature is 200-470 ℃;

the reaction time of the liquefaction reaction is not less than 15 min;

in the slurry, the content of the catalyst is 0.1-10 wt%;

the average particle size of the catalyst is 0.1 mu m-5 mm.

2. The biomass-to-liquid process according to claim 1,

the particle size of the catalyst is 5-1000 μm;

and adding a sulfur-containing compound into the catalyst until the molar ratio of the iron element to the sulfur element in the reaction system is 1 (0.5-5).

3. The biomass-to-liquid process according to claim 2, wherein the catalyst has a particle size of 5-200 μm;

the sulfur-containing compound is at least one of sulfur, hydrogen sulfide and carbon disulfide.

4. The biomass-to-liquid process according to any one of claims 1 to 3, wherein the water in the aqueous slurry is derived from water carried by the biomass itself, and the water content of the biomass is 500ppm to 20% based on the total weight of the biomass; or,

the water in the aqueous slurry is derived from externally added water.

5. The biomass-to-liquid process of claim 4,

the water content of the biomass is 2-10%;

the CO content of the CO-containing gas is not less than 15% by volume.

6. The biomass-to-liquid process of claim 5, wherein the CO-containing gas is CO and H₂Or gasifying a product gas containing CO;

the CO content of the CO-containing gas is not less than 25% by volume.

7. The biomass liquefaction process according to claim 1, characterized in that the spent desulfurization agent of ferrite compounds is spent desulfurization agent using iron oxide as active component, and Fe is used as active component_21.333O₃₂At least one of a waste desulfurizer which is an active component and a waste desulfurizer which takes FeOOH as an active component; or,

regeneration of spent desulfurization agents of said ferrite compoundsThe material is a regenerated material of waste desulfurizer using ferric oxide as active component, and the material is Fe_21.333O₃₂At least one of a regenerated product of a spent devulcanizing agent which is an active component and FeOOH.

8. The biomass-to-liquid process according to claim 7, wherein the iron oxide is ferric oxide and/or ferroferric oxide.

9. The biomass-to-liquid process of claim 8, wherein the ferric oxide is α -Fe₂O₃、α-Fe₂O₃.H₂O、γ-Fe₂O₃、γ-Fe₂O₃.H₂O, amorphous Fe₂O₃Amorphous Fe₂O₃.H₂At least one of O;

the ferroferric oxide is cubic ferroferric oxide;

10. The biomass liquefaction process according to claim 1, characterized in that the regeneration of spent desulfurization agents of ferrite compounds is a regeneration obtained by oxidizing, sulfidizing and oxidizing spent desulfurization agents of ferrite compounds by a slurry method.

11. The biomass liquefaction process of claim 10, characterized in that the regeneration process of spent desulfurization agents of ferrite compounds comprises the following steps:

adding an oxidant into the slurry to perform primary oxidation reaction;

12. The biomass liquefaction process according to claim 1, characterized in that a sulfur-containing compound is added to the catalyst so that the molar ratio of iron element to sulfur element in the reaction system is 1: (0.5-2).

13. The biomass liquefaction process of claim 12, wherein the sulfur-containing compound is added to the catalyst in a molar ratio of iron element to sulfur element in the reaction system of 1: (1-2).

14. The biomass liquefaction process according to claim 1, characterized in that the reaction time of the liquefaction reaction is between 15 and 120 min.

15. The biomass-to-liquid process according to claim 1, wherein the slurry is mixed with a CO-containing gas to carry out a liquefaction reaction, comprising the steps of:

16. The biomass-to-liquid process of claim 1, wherein the volume ratio of the CO-containing gas to the slurry is (50-10000): 1.

17. The biomass liquefaction process of claim 1, characterized in that the volume ratio of said CO-containing gas to said slurry is (100- > 5000): 1.

18. the biomass liquefaction process according to claim 1, wherein the gas containing CO is a gasified product, and can be cooled, purified, transformed, boosted and then enter the reaction system, or directly enter the reaction system.

19. The biomass liquefaction process according to claim 1, characterized in that the reaction system is carried out in a reactor, the reactor being any one of a suspended bed reactor, a slurry bed reactor, a bubble bed reactor, an ebullated bed reactor, a single pot reactor; or the reactor is one or more of a suspension bed reactor, a slurry bed reactor, a bubbling bed reactor, a boiling bed reactor and a single-kettle reactor which are connected in series or in parallel.