CN109536196B

CN109536196B - Biomass two-stage conversion process

Info

Publication number: CN109536196B
Application number: CN201811457176.4A
Authority: CN
Inventors: 林科; 郭立新; 崔永君
Original assignee: Beijing SJ Environmental Protection and New Material Co Ltd
Current assignee: Beijing Haixin Energy Technology Co ltd
Priority date: 2018-04-28
Filing date: 2018-11-30
Publication date: 2020-11-06
Anticipated expiration: 2038-11-30
Also published as: CN109536196A

Abstract

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

Description

Biomass two-stage conversion process

Technical Field

The invention belongs to the technical field of biomass utilization, energy and chemical engineering, and particularly relates to a two-stage biomass conversion 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 a biomass two-stage conversion process which has the advantages 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.

In order to solve the technical problems, the invention adopts the following technical scheme:

a biomass two-stage conversion process comprises the following steps:

preparing slurry containing the iron-based catalyst and biomass;

mixing the slurry with pure CO or CO-containing gas to perform primary conversion reaction, and collecting a conversion product;

mixing the converted product with pure CO and CO-containing gas to carry out secondary conversion reaction to prepare an oil product;

the conversion reaction is carried out under the condition that the molar ratio of the iron element to the sulfur element in the reaction system is controlled to be 1 (0.5-5), and the iron catalyst is at least one of a ferrite compound, a desulfurization waste agent of the ferrite compound or a regeneration product of the desulfurization waste agent of the iron oxide compound.

Further, the reaction pressure of the primary conversion reaction is 5-22MPa, and the reaction temperature is 100-470 ℃;

the reaction pressure of the secondary conversion reaction is 5-22MPa, and the reaction temperature is 100-470 ℃.

Further, the reaction temperature of the primary conversion reaction is 100-350 ℃, the reaction temperature of the secondary conversion reaction is 300-470 ℃, and the temperature of the primary conversion reaction is lower than that of the secondary conversion reaction.

Further, the reaction time of the primary conversion reaction is not less than 15min, preferably 15-120min, and more preferably 15-60 min;

the reaction time of the secondary conversion reaction is not less than 15min, preferably 15-120min, and more preferably 15-60 min.

Further, the slurry is mixed with pure CO or CO-containing gas to carry out primary conversion reaction, and the method comprises the following steps:

pressurizing pure CO or CO-containing gas to 5-22MPa, heating to 50-600 ℃, preferably heating to 50-450 ℃, introducing into a reaction system, and carrying out conversion reaction with slurry entering the reaction system.

pressurizing partial pure CO or CO-containing gas to 5-22MPa, heating to 50-350 ℃, introducing into the slurry, and allowing the slurry to enter a reaction system along with the slurry to perform a conversion reaction;

the rest part is pressurized to 5-22MPa and heated to 300-500 ℃, and then is introduced into the reaction system to perform conversion reaction with the slurry entering the reaction system.

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

further, after the primary conversion reaction and before the secondary conversion reaction, the method also comprises the steps of separating the conversion products and respectively collecting the light oil products and the heavy oil products.

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; alternatively, the first and second electrodes may be,

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, adding a sulfur-containing compound into the iron-based 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 sulfur-containing compound is at least one of sulfur, hydrogen sulfide and carbon disulfide. When the high-sulfur oil product is adopted to prepare slurry, the content of the sulfur element reaches the content of the iron catalyst, the molar ratio of the iron element to the sulfur element is 1 (0.5-5), and the preferable ratio is 1: (0.5-2), more preferably 1: in the case of (1-2), it is not necessary to separately prepare sulfur or a sulfur-containing compound.

Further, the water in the slurry is water carried by the organic matter, and the water content of the organic matter is 500 ppm-20%, preferably 2% -10% based on the total weight of the organic matter; or the like, or, alternatively,

the water in the slurry comes from externally added water.

Further, the CO content of the CO-containing gas is not less than 15% by volume, preferably not less than 50% by volume, most preferably not less than 90% by volume.

Further, the CO-containing gas is CO and H₂Mixed gas or synthesis gas.

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

further comprising the step of adding said iron-based catalyst and/or hydrogenation catalyst to the conversion product.

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 like, or, alternatively,

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_21.333O₃₂Regeneration of waste agents of desulphurizing agents as active components, in particular of the type FThe eOOH is at least one of the regenerants of the waste desulfurizer of the active component.

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

Further, the ferric oxide is alpha-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 average particle size of the iron-based catalyst is 0.1 to 5mm, preferably 5 to 100 μm, and most preferably 5 to 50 μm.

Further, the hydrogenation catalyst consists of a carrier and an active ingredient loaded on the carrier, wherein the loading amount of the active ingredient is 0.5-15% based on the total weight of the hydrogenation catalyst.

Further, the active component is one or more of oxides of Mo, Mn, W, Fe, Co, Ni or Pd;

the carrier is at least one of silicon dioxide, aluminum oxide, zeolite and molecular sieve.

Further, the preparation of the slurry comprises the following steps:

pretreatment of raw materials: collecting biomass, and crushing to a particle size of 0.2-5 cm;

compression: compressing and molding the crushed biomass;

and (3) secondary crushing: crushing the biomass after compression molding again to obtain biomass powder with the particle size of 0.1-500 mu m;

slurry preparation: mixing biomass powder and a flowing medium to obtain mixed slurry containing biomass particles, wherein the mass of the biomass powder accounts for 5-60% of the mixed slurry;

wherein the iron-based catalyst is added in any one of the above steps.

Further, the true density of the material after compression molding is 0.75-1.5kg/m³In the meantime.

Further, in the compression step, the compression pressure is 0.5-5MPa, and the compression temperature is 30-60 ℃.

Further, the dosage of the iron-based catalyst is 0.1-10% of the slurry.

Further, the grinding pulping is stirring pulping, dispersing pulping, emulsifying pulping, shearing pulping, homogenizing pulping or colloid milling pulping.

Further, the biomass is one or more of crop straws, wood chips, oil residues, leaves or algae;

further, the flowing medium is oil, water or an oil-water mixture, and can be waste water, waste oil or inferior oil and the like in life or industrial production, wherein the waste oil or inferior oil can be one or more of illegal cooking oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, wash oil and anthracene oil.

The invention also provides another slurry preparation method, and the slurry preparation method comprises the following steps:

compression: compressing and molding the crushed biomass;

filling pores: mixing the biomass powder with oil, wherein the amount of the oil is 40-100% of the mass of the biomass powder;

slurry preparation: mixing the obtained mixture with water, wherein the amount of the water is 0.1-10% of the mass of the biomass powder, and grinding and pulping to obtain aqueous slurry;

wherein the iron-based catalyst is added in any one of the above steps.

Further, the oil used was added in two portions, and the pores were filled: mixing the biomass powder with partial oil, wherein the use amount of the partial oil is 10-40% of the mass of the biomass powder;

slurry preparation: mixing the obtained mixture with water, wherein the amount of the water accounts for 0.1-10% of the mass of the biomass powder, then mixing with the residual oil, and grinding and pulping to obtain slurry;

wherein the mass of the biomass accounts for 10-60% of the total mass of the mixed slurry.

The technical scheme of the invention has the following advantages:

1. the biomass two-stage conversion 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 an iron-based catalyst, adopts slurry, and simultaneously controls the molar ratio of iron elements to sulfur elements in a reaction system, finds that the carbonylation can be effectively utilized to block the free radical polycondensation of organic matters in the cracking process in the presence of CO, and the conversion active hydrogen hydrogenation of CO and water is realizedThe conversion reaction can be realized, water can be additionally added into the biomass liquid or the mineral oil, the heat productivity of the prepared oil product can be improved while the liquefaction yield is improved, and a large amount of wastewater can not be generated after the conversion reaction is finished. At least two times of conversion reaction is adopted, and different means such as temperature, pressure, atmosphere, heat supply mode, cooling mode, intermediate material separation and the like can be flexibly adjusted according to materials with different properties and different product requirements. Light materials can be separated out between two stages of conversion reaction, and heavy materials are sent to the next stage for continuous conversion reaction; specifically, the reaction pressure of the preceding stage conversion reaction is high, the reaction pressure of the subsequent stage conversion reaction is low, or the reaction pressure of the preceding stage conversion reaction is low, and the reaction pressure of the subsequent stage conversion reaction is high; the gases of the two-stage conversion reaction can be different, and the gas of the preceding conversion reaction is pure CO or gas containing CO, wherein CO and H in the gas containing CO₂The proportion of the gas components and the amount of the gas can be adjusted according to the reaction condition; the two-stage conversion reaction can adopt different catalysts or different catalysts. In short, the main characteristics of the separate secondary conversion reactions are that the reaction temperatures are the same or different, the reaction pressures can be the same or different, the catalysts provided can be the same or different, and the composition of the gas mixture of the reactions can be the same or different, greatly improving the flexibility of operation.

2. According to the biomass two-stage conversion process provided by the invention, the reaction temperature of the primary conversion reaction is 100-350 ℃, the reaction temperature of the secondary conversion reaction is 300-470 ℃, the temperature of the primary conversion reaction is lower than that of the secondary conversion reaction, the primary conversion reaction is mild, carbonylation, cracking and the like are dominant, the secondary conversion reaction is severe, and the conversion and hydroisomerization and the like are dominant, so that the conversion effect of organic matters is improved.

3. The invention provides a biomass two-stage conversion process, and further, a waste desulfurization agent of a ferrite compound is a waste desulfurization agent taking 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; the regenerated material of waste desulfurizing agent of ferrite compound is activated by using iron oxideRegenerant of waste desulfurizer of chemical composition, and use of regenerated desulfurizer of chemical composition as Fe_21.333O₃₂The catalyst is used to be mixed with proper amount of sulfur, the catalyst is firstly combined with CO to form carbonyl compound under the atmosphere of CO, then carbon atoms are grafted on micromolecule active sites formed after organic matters (such as biomass and the like) are thermally cracked through the carbonyl compound, 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 organic matters and the oil product yield of long molecular chain to micromolecule transformation 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 which iron oxide compound and iron sulfur compound crystal phase undergo reconstitution and transformation, plus S^2-The ionic radius (0.18nm) is larger than O^2-The ionic radius (0.14nm), so with the conversion 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 material obtained by the method has small particle size and good lipophilicity, the structure of the regenerated material is a flaky nano structure, and the adsorbed sulfur between the sheets is blocked, so that the agglomeration of the regenerated material is avoided, and the regenerated material is greatly agglomeratedThe adsorption capacity of CO is improved, and the carbonylation, hydrogen production by conversion and hydrogenation catalytic capacity are enhanced.

4. The invention provides a biomass two-stage conversion process, which comprises the steps of firstly crushing collected biomass to the particle size of 0.2-5cm by a specific slurry preparation method of aqueous slurry; compressing and molding the crushed biomass; crushing the biomass after compression molding again to obtain biomass powder with the particle size of 0.1-500 mu m; in the process, biomass does not need to be dried, so that the energy consumption is reduced; through the matching of the steps, especially the control of granularity in the two crushing steps and the control of the compression and grinding pulping steps, biomass material particles can be mechanically inlaid under the mechanical action, the structures of cellulose and lignin are damaged and intertwined, the pores among the particles are greatly reduced, the materials are tightly combined, a large amount of air in the pores is removed, loose biomass solids are subjected to the stages of rearrangement, mechanical deformation such as collapse, closure and the like, and the volume of the biomass solids is greatly reduced, so that the porosity of the biomass can be reduced, the density and the specific gravity of the biomass can be increased, and the biomass material particles are favorable for pulping. Meanwhile, the increase of the concentration of the biomass solids in the slurry also inevitably increases the conveying capacity of the pump to the biomass solids in unit time, thereby 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, and the waste is changed into valuable.

According to the process, the biomass powder is mixed with the pore filling oil, so that the oil is filled into the pores or pore passages of the biomass powder, and then the oil and water are mixed for pulping, so that water is prevented from entering the pores or pore passages of the biomass, the biomass content of the slurry obtained by the invention is improved, the viscosity of the slurry is reduced, the fluidity is good, the slurry is convenient to convey, the feeding requirement of a subsequent treatment process is met, the utilization efficiency of a device is improved, the process is simple, no additional additive is needed, the using amount of an oily flowing medium is saved, and the process is economical and environment-friendly. The biomass and the pore filling oil are mixed under the negative pressure condition, so that the oil can be quickly filled into the pores or pore passages of the biomass powder, water is further prevented from entering the pores or pore passages of the biomass, and the fluidity of the slurry is improved.

According to the process, biomass powder is mixed with pore filling oil, so that the oil is filled into pores or pore passages of the biomass powder, and then the oil is mixed with water for pulping, so that biomass slurry can form a system of straw in oil and oil in water, wherein the system has two characteristics in the subsequent reaction process, firstly, water in the biomass slurry can be subjected to in-situ hydrogen production reaction, hydrogen is more soluble in the oil due to the fact that the hydrogen is more soluble in water, and the generated hydrogen is soluble in the oil, so that the biomass can be promoted to contact with the hydrogen for reaction, and the reaction performance of the biomass is improved; and secondly, gas in the pore canal of the solid biomass particles is completely infiltrated by oil, so that the heat exchange efficiency of the porous medium and the heat and mass transfer performance of the system during reaction are improved, the reactivity of the material is enhanced, and the yield of the liquid product is improved. The biomass is firstly mixed with a small part of pore filling oil, and then is mixed with water and solvent oil, so that the diffusion of hydrogen generated in situ can be avoided, the hydrogen concentration around the biomass is improved, and the reaction performance of the biomass is further improved.

5. The biomass two-stage conversion process provided by the invention regulates and controls the bulk density of biomass which is subjected to primary crushing and compression to be not less than 0.7g/cm³Regulating and controlling the average particle size of the biomass subjected to secondary crushing to 0.1-500 mu m, and adding the biomass into a solvent for grinding and pulping conveniently by the regulation and control mode so as to improve the solid content of the biomass in the pulp;

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.

6. The biomass two-stage conversion process provided by the invention comprises the steps of conveying reaction raw materials and CO-containing gas into a reactor, and carrying out reactions such as cracking, carbonylation, transformation, hydrogenation and the like 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 unconverted organic matters in the reactor and the balanced discharge of the catalyst, ensuring the full progress of various reactions, and being beneficial to improving the conversion rate of the organic matters and the yield of the bio-oil

7. According to the biomass two-stage conversion process provided by the invention, organic matters do 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 CO-containing gas and adopting the action of a cheap iron-based catalyst or a waste agent, sufficient free radicals are easily provided, carbonization and coking of organic matters are avoided, the conversion rate of the organic matters 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 following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

The embodiment provides a biomass two-stage conversion process, which comprises the following steps:

iron-based catalyst:

the iron 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 slurry:

(1) collecting corn stalks with the water content of 5-20 wt%, and then crushing the corn stalks to the grain size of 0.2-5cm by using an ultrafine crusher;

(2) compressing and molding the straw crushed in the step (1) by a plodder, wherein the compression pressure is 2.5MPa, the compression temperature is 45 ℃, and the straw is compressed to the true density of 1.0kg/m³；

(3) Crushing the straws compressed and molded in the step (2) again by using a jet mill until the particle size is 0.1-500 mu m to obtain straw powder;

(4) and (3) uniformly mixing 80kg of waste lubricating oil, 6kg of the iron-based catalyst and 100kg of straw powder, wherein the average particle size of the added iron-based catalyst is 10 mu m, and obtaining slurry.

Primary conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the mixture is pressurized to 17MPa, the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 17MPa and heated to 450 ℃, the mixture is injected into a suspension bed reactor from a reaction inlet of the suspension bed and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the reactor, the reaction pressure of the conversion reaction is controlled to be 16MPa, the reaction temperature is controlled to be 300 ℃, the reaction time is 30min, and CO and H are reacted for 30min₂The volume ratio of the mixed gas to the slurry is 2000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

dividing synthetic gas (the volume ratio of CO is 50%) into two parts, wherein one part is pressurized to 16MPa and heated to 350 ℃, then introduced into a pipeline for conveying a conversion product, the other part is pressurized to 16MPa and heated to 500 ℃, then injected into a slurry bed reactor from an inlet of the slurry bed reactor, and undergoes cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the slurry bed reactor, the reaction pressure of the secondary conversion reaction is controlled to be 15MPa, the reaction temperature is 400 ℃, the reaction time is 60min, the volume ratio of the synthetic gas (the volume ratio of CO is 50%) to the conversion product is 2000: 1, preparing an oil product.

Example 2

iron-based catalyst:

the iron catalyst is amorphous FeOOH; adding sulfur: adding solid sulfur powder into the iron-based catalyst until the molar ratio of iron element to 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:

(3) Crushing the straws compressed and molded in the step (2) again by using a jet mill until the particle size is 0.1-500 microns to obtain straw powder;

(4) and (3) mixing 110kg of waste lubricating oil, 100kg of straw powder obtained in the step (3) and 6kg of the iron-based catalyst, and grinding and pulping by using a colloid mill for 15 minutes to obtain slurry.

Primary conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the slurry is pressurized to 17MPa and heated to 250 ℃, and then the slurry is introduced into a pipeline for conveying the slurry, and the rest of the slurry is pressurized to 17MPa and heated to 350 ℃, and then the slurry is mixed with the waterInjecting the slurry into a fluidized bed reactor at an inlet of the fluidized bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the fluidized bed reactor, controlling the reaction pressure of the conversion reaction to be 16MPa, the reaction temperature to be 270 ℃, the reaction time to be 35min, and reacting CO and H₂The volume ratio of the mixed gas to the slurry is 1000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

firstly, adding an iron catalyst into a conversion product, wherein the iron catalyst is amorphous iron oxyhydroxide, and the adding amount of the amorphous iron oxyhydroxide is 0.5 wt% of the mass of the conversion product;

pressurizing the synthesis gas (the volume ratio of CO is 50 percent) to 15.4MPa, heating to 380 ℃, injecting the synthesis gas into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the slurry bed reactor, controlling the reaction pressure of the secondary conversion reaction to be 15MPa, the reaction temperature to be 425 ℃, the reaction time to be 45min, and the volume ratio of the synthesis gas (the volume ratio of CO is 50 percent) to the conversion product to be 1500: 1, preparing an oil product.

Example 3

iron-based catalyst:

the iron catalyst is a regeneration product of a waste desulfurizer agent which takes iron oxyhydroxide as an active component, wherein the total mass of the desulfurizer taking the iron oxyhydroxide as the active component is 30g of alpha-FeOOH, 20g of amorphous iron oxyhydroxide, 8g of potassium oxide and 10g of kaolin serving as a binder;

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;

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

preparing slurry:

(1) collecting corn straw and cotton straw with water content of 5-20 wt%, and pulverizing with superfine pulverizer to particle size of 0.2-5 cm;

(2) compressing and molding the crushed straws obtained in the step (1) by a plodder, wherein the compression pressure is 4MPa, the compression temperature is 40 ℃, and the compression is carried out until the true density is 0.9kg/m³；

(3) Crushing the straws compressed and molded in the step (2) again by using a jet mill to obtain straw powder with the particle size of 0.1-500 microns, weighing 100kg of straw powder, mixing the straw powder with 1kg of the iron-based catalyst to obtain mixed powder, wherein the average particle size of the added regeneration product of the waste agent of the desulfurizer with the FeOOH as the active component is 20 microns;

(4) then mixing with 100kg of rancid oil, and grinding and pulping by adopting a colloid mill for 15 minutes to obtain slurry.

Adding sulfur: adding solid sulfur powder into the regenerated product of the waste agent 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 the reaction system is 1: 2.5;

primary conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 80% and H)₂20 percent) of the mixture is pressurized to 19.5MPa and heated to 200 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 19.3MPa and heated to 380 ℃, then the mixture is injected into the slurry bed reactor from 3 injection ports on the bottom and the side wall of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry bed reactor, the reaction pressure is controlled to be 19MPa, the reaction temperature is controlled to be 350 ℃, the reaction time is 20min, and the CO and the H undergo cracking, carbonylation, transformation and hydrogenation reaction₂The volume ratio of the mixed gas to the slurry is 800: 1, collecting a conversion product;

and (3) secondary conversion reaction:

adding a hydrogenation catalyst into a conversion product, wherein the hydrogenation catalyst comprises zeolite and MoO, NiO and CoO loaded on the zeolite, and based on the total weight of the hydrogenation catalyst, the loading capacity of the MoO is 2%, the loading capacity of the NiO is 6%, the loading capacity of the MoO is 3%, and the adding amount of the hydrogenation catalyst is 2 wt% of the mass of the conversion product;

then CO and H are reacted₂Mixed gas (CO 20% and H)₂80 percent) into two parts, one part is pressurized to 20MPa and heated to 380 ℃, then the two parts are introduced into a pipeline for conveying conversion products, the other part is pressurized to 20MPa and heated to 480 ℃, then the mixture is injected into a slurry bed reactor from an inlet of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the conversion products entering the slurry bed reactor, the reaction pressure of the secondary conversion reaction is controlled to 15MPa, the reaction temperature is 390 ℃, the reaction time is 30min, CO and H react₂Mixed gas (CO 20% and H)₂80% by volume) to the conversion product is 4000: 1, preparing an oil product.

Example 4

iron-based catalyst:

the iron-based catalyst is a regeneration product of a waste agent of a desulfurizer taking iron oxide as an active component, wherein in the desulfurizer taking the iron oxide as the active component, 12g of cubic ferroferric oxide and amorphous Fe₂O₃24g of amorphous Fe₂O₃.H₂O39g and NiO were 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: 2;

preparing slurry:

(1) collecting red algae, air drying until water content is lower than 20 wt%, and pulverizing to particle size of 0.2-5 cm;

(2) mixing the powder obtained in the step (1)Compressing the crushed red algae with a tablet press at 40 deg.C under 3MPa to true density of 0.95kg/m³；

(3) Crushing the red algae compressed and molded in the step (2) again by using an airflow crusher until the particle size is 100-200 microns to obtain red algae powder;

(4) and (3) mixing 100kg of the red algae powder crushed in the step (3) with 200kg of waste engine oil and 16kg of iron-based catalyst water, grinding and pulping for 12min to obtain slurry, wherein the average particle size of the added iron-based catalyst is 2 mu m.

Primary conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the total amount of the components, pressurizing to 20.4MPa, heating to 400 ℃, injecting the mixture into the slurry bed reactor through 3 injection ports on 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 20MPa, the reaction temperature to be 300 ℃, the reaction time to be 30min, and reacting CO and H for 30min₂The volume ratio of the mixed gas to the slurry is 650: 1, collecting a conversion product;

and (3) secondary conversion reaction:

firstly, adding the iron-based catalyst in the embodiment into the conversion product, wherein the adding amount of the iron-based catalyst is 1.9 wt% of the mass of the conversion product;

then CO and H are reacted₂Mixed gas (CO volume ratio of 30%, H)₂70 percent of the total volume of the components in the slurry bed reactor), pressurizing to 19MPa, heating to 490 ℃, injecting into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the reactor, controlling the reaction pressure of the secondary conversion reaction to be 18MPa, the reaction temperature to be 440 ℃, the reaction time to be 30min, and controlling the reaction pressure of CO and H to be 18MPa₂Mixed gas (CO volume ratio of 30%, H)₂70%) to the conversion product in a volume ratio of 1000: 1, preparing an oil product.

Example 5

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

iron-based catalyst:

the iron catalyst is a waste desulfurizer using FeOOH as an active component, wherein 70g of amorphous iron oxyhydroxide and Co in the desulfurizer using FeOOH as the active component₂O₃25g 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 slurry:

(1) collecting peanut oil residues, wherein the water content of the peanut oil residues is 5-15 wt%, and then crushing the peanut oil residues to the particle size of 0.2-5cm by using an ultrafine crusher;

(2) compressing and molding the peanut oil residue crushed in the step (1) by a plodder, wherein the compression pressure is 2.5MPa, the compression temperature is 50 ℃, and the compression is carried out until the true density is 1.2kg/m³；

(3) Crushing the peanut oil residue compressed and molded in the step (2) again by using a jet mill until the particle size is 0.1-500 microns to obtain peanut oil residue powder;

(4) and (3) uniformly mixing 150kg of illegal cooking oil, 100kg of peanut oil residue powder obtained in the step (3) and 5kg of the iron-based catalyst, wherein the average particle size of the added waste desulfurizer taking FeOOH as an active component is 120 microns, so as to obtain slurry.

Primary conversion reaction:

pressurizing part of pure CO gas to 18MPa, heating to 250 ℃, introducing the pure CO gas into the slurry, pressurizing the rest part of the pure CO gas to 18MPa, heating to 500 ℃, injecting the rest part of the pure CO gas into the slurry bed reactor from 4 injection ports on the bottom and the side wall of the slurry bed reactor, and performing cracking, carbonylation, transformation and hydrogenation reaction on the pure CO gas and the slurry entering the slurry bed reactor, controlling the reaction pressure to be 17MPa, the reaction temperature to be 310 ℃, the reaction time to be 20min, wherein the volume ratio of the pure CO gas to the slurry is 950: 1, collecting a conversion product;

and (3) secondary conversion reaction:

pressurizing the synthesis gas (the volume ratio of CO is 70 percent) to 14MPa, heating to 480 ℃, injecting the synthesis gas into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the slurry bed reactor, controlling the reaction pressure of the secondary conversion reaction to be 20MPa, the reaction temperature to be 380 ℃, the reaction time to be 30min, and the volume ratio of the synthesis gas (the volume ratio of CO is 70 percent) to the conversion product to be 1500: 1, preparing an oil product.

Example 6

iron-based catalyst:

the iron-based catalyst is a waste agent of a desulfurizer taking FeOOH as an active component, wherein soluble iron salt Fe (NO) 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 1:2, doping solid sulfur powder into the iron-based catalyst until the molar ratio of the iron element to the sulfur element is 1:2, thereby ensuring that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 2;

if the molar ratio of the iron element to the sulfur element is more than 1:2, redundant sulfur can be removed by conventional ways such as solvent extraction or heating for sulfur melting;

preparing slurry:

(1) collecting 100kg of peanut oil residue with water content of 5-15 wt%, and pulverizing with an ultrafine pulverizer to particle size of 0.2-5 cm;

(2) mixing the crushed peanut oil residue in the step (1) with 8kg of catalyst, and performing compression molding by adopting a plodder, wherein the compression pressure is 2.5MPa, the compression temperature is 50 ℃, and the compression is performed until the true density is 1.2kg/m³；

(3) Crushing the material compressed and molded in the step (2) again by using a jet mill until the particle size is 0.1-500 microns to obtain mixed powder of the peanut oil residue and the catalyst;

(4) mixing 90kg of illegal cooking oil with the mixed powder of the step (3) under the negative pressure of 30 KPa;

(5) and (3) mixing the mixture obtained in the step (4) with 8kg of water, and grinding and pulping by using a colloid mill for 16 minutes to obtain slurry, wherein the average particle size of the added iron catalyst is 5 microns.

Primary conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the mixture is pressurized to 5.7MPa and heated to 400 ℃, the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 5.2MPa and heated to 400 ℃, the mixture is injected into a slurry bed reactor from an inlet of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry, the reaction pressure of the transformation reaction is controlled to be 5MPa, the reaction temperature is controlled to be 340 ℃, the reaction time is 90min, and CO and H are reacted with each other₂The volume ratio of the mixed gas to the slurry is 8000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

firstly, adding the iron-based catalyst in the embodiment into the conversion product, wherein the adding amount of the iron-based catalyst is 1 wt% of the mass of the conversion product;

then CO and H are reacted₂Mixed gas (CO volume ratio of 60%, H)₂40 percent), pressurizing to 19MPa, heating to 480 ℃, injecting into the slurry bed reactor from the inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the slurry bed reactor, controlling the reaction pressure of the secondary conversion reaction to be 18MPa, the reaction temperature to be 370 ℃, the reaction time to be 30min, and reacting CO and H₂Mixed gas (CO volume ratio of 60%, H)₂40%) to the conversion product at 7000: 1, preparing an oil product.

Example 7

iron-based catalyst:

the iron-based catalyst is a regeneration 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 converting 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 material₄Extracting the filtered solid material, co-extractingAnd combining the extraction liquid for three times, recovering the solvent by using a distillation method, simultaneously obtaining crystallized elemental sulfur, and mixing the residual solid after the extraction liquid is separated out 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 iron-based 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:

(1) collecting wheat straw and peanut straw with water content of 8-20 wt%, and pulverizing with superfine pulverizer to particle size of 0.2-5 cm;

(2) compressing and molding the straw crushed in the step (1) by a plodder, wherein the compression pressure is 5MPa, the compression temperature is 30 ℃, and the straw is compressed to the true density of 1.5kg/m³；

(4) mixing 10kg of the catalyst with 80kg of anthracene oil, and then mixing with 100kg of straw powder obtained in the step (3);

(5) and (3) mixing the straw powder mixture obtained in the step (4) with 3kg of water, and grinding and pulping by using a colloid mill for 20 minutes to obtain slurry, wherein the average particle size of the added iron-based catalyst is 5 mm.

Primary conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the mixture is pressurized to 16.8MPa and heated to 250 ℃, the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 16.2MPa and heated to 450 ℃, the mixture is injected into a fluidized bed reactor from an inlet of the fluidized bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the fluidized bed reactor, the reaction pressure of the transformation reaction is controlled to be 16MPa, the reaction temperature is controlled to be 350 ℃, the reaction time is 60min, and CO and H are reacted with each other₂The volume ratio of the mixed gas to the slurry is5000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

directly pressurizing carbon monoxide to 19MPa, heating to 410 ℃, injecting the carbon monoxide into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the slurry bed reactor, controlling the reaction pressure of the secondary conversion reaction to be 18MPa, the reaction temperature to be 420 ℃, the reaction time to be 30min, and H₂Volume ratio to conversion product 2600: 1, preparing an oil product.

Example 8

iron-based catalyst:

the iron-based catalyst contains Fe_21.333O₃₂Wherein the regeneration product of the spent agent of the desulfurizing agent of (1), wherein the regenerated product contains Fe_21.333O₃₂In the desulfurizing agent of (1), magnetic iron oxide red Fe_21.333O₃₂55g of copper oxide, 12g of carrier ferric oxide and 21g of carrier ferric oxide;

the desulfurization process of the coal pyrolysis gas containing the hydrogen sulfide by the iron-based catalyst is as follows:

(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;

(2) the desulfurizer becomes waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the desulfurizer containing Fe in the application_21.333O₃₂The waste agent of the desulfurizing agent of (1);

above-mentioned Fe-containing_21.333O₃₂The method for regenerating the waste desulfurizer comprises the following steps:

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

2) heating the slurry to 60 ℃ under normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, controlling the flow to be 500mL/min, and magnetically stirring to promote the reaction for 10 min;

3) after the reaction is finished, filtering reaction liquid, washing the obtained precipitate for 2 times by using water, and naturally drying to obtain a regenerated substance of the waste agent;

preparing slurry:

(1) collecting 100kg of corn straws and cotton straws with the water content of 5-20 wt%, mixing with 5kg of catalyst, and pulverizing to obtain particles with the particle size of 0.2-5cm by using an ultrafine pulverizer;

(2) compressing and molding the crushed material in the step (1) by a plodder, wherein the compression pressure is 4MPa, the compression temperature is 40 ℃, and the material is compressed to the true density of 0.9kg/m³；

(3) Crushing the mixed material compressed and molded in the step (2) again by using a jet mill until the particle size is 0.1-500 microns to obtain mixed powder of straws and a catalyst;

(4) mixing 30kg of rancid oil with the mixed powder of step (3) under a negative pressure of 100 KPa;

(5) and (3) mixing the mixture obtained in the step (4) with 50kg of rancid oil, finally mixing with 2kg of water, and grinding and pulping by using a colloid mill for 15 minutes to obtain slurry, wherein the average particle size of the added iron-based catalyst is 300 mu m.

Primary conversion reaction:

pressurizing part of pure CO to 5.7MPa, heating to 250 ℃, introducing the pure CO into a pipeline for conveying the slurry, pressurizing the rest part of the pure CO to 5.2MPa, heating to 300 ℃, injecting the pure CO into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the slurry bed reactor, and introducing hydrogen sulfide gas into the slurry bed reactor in the conversion process, so as to ensure that the molar ratio of iron element to sulfur element in the reaction system is 1:3, and controlling the reaction pressure of the conversion reaction to be 5MPa, the reaction temperature to be 270 ℃, the reaction time to be 90min, wherein CO and H are mixed with the raw materials₂The volume ratio of the mixed gas to the slurry is 3000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

pressurizing the synthetic gas (the volume ratio of CO is 39%) to 16MPa, heating to 400 ℃, injecting the synthetic gas into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the converted product entering the slurry bed reactor, controlling the reaction pressure of the secondary conversion reaction to be 15MPa, the reaction temperature to be 360 ℃, the reaction time to be 40min, and controlling the volume ratio of the synthetic gas (the volume ratio of CO is 39%) to the converted product to be 6000: 1, preparing an oil product.

Comparative example 1 (one conversion)

This comparative example provides a biomass conversion process with the same iron based catalyst source and slurry formulation as in example 4, except that the conversion reaction was carried out in the following specific steps: reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the total amount of the components, pressurizing to 20.4MPa, heating to 500 ℃, injecting the mixture into the slurry bed reactor through 3 injection ports on 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 20MPa, the reaction temperature to be 410 ℃, the reaction time to be 30min, and reacting CO and H for 30min₂The volume ratio of the mixed gas to the slurry is 650: 1, preparing an oil product.

Comparative example 2 (drying, molar ratio of iron element to sulfur element in reaction System 1:0.1)

This comparative example provides a biomass conversion process that is the same as example 7, except that: in the comparative example, the wheat and peanut 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.

Examples of the experiments

The distribution of the products prepared using the processes of examples 1-8 of the present invention was compared to comparative examples 1-2 and the products were tested as follows:

the percent solid organic matter conversion is (the total mass of solid organic matter in the raw material-the mass of solid organic matter remaining in the reaction product)/the total mass of solid organic matter in the raw material, and the solid organic matter in the percent solid organic matter conversion refers to anhydrous and ashless groups (the same applies hereinafter);

the yield percent of the solid organic matter converted oil is the mass of the liquid phase oil product at normal temperature and normal pressure in the product converted from the solid organic matter/the total feeding mass of the solid organic matter 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 table 1:

table 1 comparison of conversion effect of solid organic matter

The data in the table show that the indexes of the solid organic matter conversion rate, the solid organic matter conversion oil yield, the solid organic matter conversion oil phase oxygen content, the solid organic matter conversion oil calorific value and the like in the embodiment of the invention are better than those in the comparative example. From the comparison of data between the examples, it can be seen that the above criteria can be further improved by a particular slurry preparation process by filling the voids of the biosolid material.

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 of the invention may be made without departing from the spirit or scope of the invention.

Claims

1. A biomass two-stage conversion process, characterized by comprising the steps of:

preparing slurry containing an iron catalyst and biomass;

mixing the converted product with pure CO or CO-containing gas to carry out secondary conversion reaction to prepare an oil product, wherein the temperature of the primary conversion reaction is lower than that of the secondary conversion reaction;

and adding a sulfur-containing compound or elemental sulfur into the iron-based catalyst until the molar ratio of the iron element to the sulfur element in the reaction system is 1 (0.5-5), wherein the iron-based catalyst is at least one of a ferrite compound, a desulfurization waste agent of the ferrite compound or a regeneration of the desulfurization waste agent of the iron oxide compound.

2. The two-stage biomass conversion process as claimed in claim 1, wherein the reaction pressure of the primary conversion reaction is 5-22MPa, and the reaction temperature is 100-470 ℃;

3. The two-stage biomass conversion process as claimed in claim 2, wherein the reaction temperature of the first conversion reaction is 100-350 ℃ and the reaction temperature of the second conversion reaction is 300-470 ℃.

4. A process for the two-stage conversion of biomass according to any one of claims 1 to 3, characterized in that the reaction time of one conversion reaction is not less than 15 min;

the reaction time of the secondary conversion reaction is not less than 15 min.

5. The two-stage biomass conversion process according to claim 4, wherein the slurry is mixed with pure CO or CO-containing gas to perform a primary conversion reaction, comprising the steps of:

pressurizing pure CO or CO-containing gas to 5-22MPa, heating to 50-450 ℃, introducing into a reaction system, and carrying out conversion reaction with the slurry entering the reaction system.

6. The two-stage biomass conversion process according to claim 5, wherein the slurry is mixed with pure CO or CO-containing gas to perform a primary conversion reaction, comprising the steps of:

7. The two-stage biomass conversion process according to claim 6, wherein the volume ratio of pure CO or CO-containing gas to slurry is (50-10000): 1.

8. The two-stage biomass conversion process according to claim 4, further comprising the steps of separating the conversion products and collecting the light oil products and the heavy oil products after the primary conversion reaction and before the secondary conversion reaction.

9. The two-stage biomass conversion process according to claim 4, wherein 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, an ebullated bed reactor and a single-pot reactor; alternatively, the first and second electrodes may be,

10. The two-stage biomass conversion process according to claim 4, wherein a sulfur-containing compound or elemental sulfur is added to the iron-based catalyst until the molar ratio of iron element to sulfur element in the reaction system is 1: (0.5-2).

11. The two-stage biomass conversion process according to claim 10, wherein the sulfur-containing compound is at least one of hydrogen sulfide and carbon disulfide.

12. The two-stage biomass conversion process according to claim 10 or 11, wherein the water in the slurry is derived from water carried by the biomass itself, and the water content of the biomass is 500 ppm-20% based on the total weight of the biomass; or the like, or, alternatively,

the water in the slurry comes from externally added water.

13. The two-stage biomass conversion process according to claim 12, wherein the CO-containing gas has a CO content of not less than 15% by volume.

14. The two-stage biomass conversion process according to claim 13, wherein the CO-containing gas is CO and H₂Mixed gas or synthesis gas.

15. The two-stage biomass conversion process according to claim 14, further comprising the step of adding said iron-based catalyst and/or hydrogenation catalyst to the conversion product.

16. The two-stage biomass conversion process according to claim 15, wherein the spent desulfurization agent of the ferrite compound is a spent desulfurization agent using iron oxide as an active component, and Fe is used as the 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 the like, or, alternatively,

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.

17. The two-stage biomass conversion process according to claim 16, wherein the iron oxide is ferric oxide and/or ferroferric oxide.

18. The two-stage biomass conversion process according to claim 17, 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;

19. The two-stage biomass conversion process according to claim 18, wherein the regenerated material of spent desulfurization reagent of ferrite compounds is a regenerated material obtained by oxidizing, sulfurizing and oxidizing spent desulfurization reagent of ferrite compounds by a slurry method.

20. The two-stage biomass conversion process according to claim 19, wherein the regeneration method of the spent desulfurization agent of the ferrite compound comprises the following steps:

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

21. The two-stage biomass conversion process according to claim 20, wherein the iron-based catalyst has an average particle size of 0.1 μm to 5 mm.

22. The two-stage biomass conversion process according to claim 15, wherein the hydrogenation catalyst comprises a support and an active ingredient supported thereon, wherein the active ingredient is present in an amount of 0.5 to 15% by weight based on the total weight of the hydrogenation catalyst.

23. The two-stage biomass conversion process according to claim 22, wherein the active ingredient is one or more of oxides of Mo, Mn, W, Fe, Co, Ni or Pd;

24. The two-stage biomass conversion process according to claim 4, wherein the slurry is formulated to include the steps of:

compression: compressing and molding the crushed biomass;

slurry preparation: mixing biomass powder with a flowing medium to obtain mixed slurry containing biomass particles, wherein the mass of the biomass powder accounts for 10-60% of the mixed slurry;

wherein the iron-based catalyst is added in any one of the above steps.

25. The two-stage biomass conversion process according to claim 24, wherein the true density of the compression molded material is 0.75-1.5kg/m³In the meantime.

26. The two-stage biomass conversion process according to claim 24, wherein in the compressing step, the compression pressure is 0.5-5MPa and the compression temperature is 30-60 ℃.

27. The two-stage biomass conversion process according to claim 24, wherein the iron-based catalyst is used in an amount of 0.1-10% of the slurry.

28. The two-stage biomass conversion process according to claim 24, wherein the slurry preparation is stirring pulping, dispersing pulping, emulsifying pulping, shearing pulping, homogenizing pulping or colloid milling pulping.

29. A two-stage biomass conversion process according to any one of claims 24 to 28, wherein the biomass is one or more of crop straw, wood chips, oil residues, leaves or algae;

the flowing medium is oil or water, and the oil is one or more of illegal cooking oil, rancid oil, waste lubricating oil and heavy oil.

30. The two-stage biomass conversion process according to claim 4, wherein the reaction time of one conversion reaction is 15-60 min;

the reaction time of the secondary conversion reaction is 15-120 min.

31. The two-stage biomass conversion process according to claim 7, wherein the volume ratio of pure CO or CO-containing gas to slurry is (100- & 5000): 1.

32. the two-stage biomass conversion process according to claim 10, wherein a sulfur-containing compound or elemental sulfur is added to the iron-based catalyst until the molar ratio of iron element to sulfur element in the reaction system is 1: (1-2).

33. The two-stage biomass conversion process according to claim 12, wherein the water in the slurry is derived from water carried by the biomass itself, and the water content of the biomass is 2-10% based on the total weight of the biomass.

34. The two-stage biomass conversion process according to claim 21, wherein the iron-based catalyst has an average particle size of 5 μm to 100 μm.