阅读说明：本技术 一种生物质二级转化工艺 (Secondary biomass conversion process ) 是由 林科 郭立新 于 2018-12-04 设计创作，主要内容包括：本发明属于生物质利用、能源、化工技术领域,具体涉及一种生物质二级转化工艺。该转化工艺采用铁氧化合物、铁氧化合物的脱硫废剂或铁氧化合物的脱硫废剂的再生物中的至少一种作为催化剂,并采用含水浆液,同时控制反应体系中铁元素与硫元素的摩尔比,发现在CO存在下能有效地利用羰基化阻断有机质在裂解过程中的自由基缩聚,并实现CO和水的变换活性氢加氢,在该转化反应中,有机质特别是生物质固体无需脱水、可直接进行转化反应,生物质液体或矿物油中可额外加入水,在提高液化收率的同时,还能提高所制得油品的发热量,转化反应结束后,不会产生大量废水。(The invention belongs to the technical field of biomass utilization, energy and chemical engineering, and particularly relates to a secondary biomass conversion process. The conversion 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 mole 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 organic matter in the cracking process in the presence of CO, and the conversion active hydrogen hydrogenation of CO and water can be realized.)

1. A secondary biomass conversion process is characterized by comprising the following steps:

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

compression: compressing and molding the crushed biomass;

and (3) secondary crushing: crushing the compressed and molded biomass again to obtain biomass powder with the particle size of 80-120 meshes;

mixing biomass powder with oil and water, wherein the biomass powder accounts for 10-60% of the mixed mass, and the water accounts for 0.1-10% of the biomass powder, and grinding and pulping to obtain aqueous slurry;

adding an iron-based catalyst in any one of the steps;

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

mixing the converted product with hydrogen to perform a secondary conversion reaction to prepare an oil product;

the iron-based catalyst is at least one of ferrite compounds, waste desulfurization agents of the ferrite compounds or regenerated substances of the waste desulfurization agents of the iron oxide compounds; and controlling the molar ratio of the iron element to the sulfur element in the reaction system to be 1 (0.5-5).

2. The secondary biomass conversion process according to claim 1, wherein the sulfur-containing compound is added to the iron-based catalyst until the molar ratio of iron element to sulfur element in the reaction system is 1 (0.5-5), preferably 1: (0.5-2), more preferably 1: (1-2).

3. The secondary biomass conversion process according to claim 2, wherein the sulfur-containing compound is at least one of sulfur, hydrogen sulfide, and carbon disulfide.

4. The secondary biomass conversion process according to any one of claims 1 to 3, wherein the iron-based catalyst is contained in the aqueous slurry in an amount of 0.1 to 10 wt%.

5. The secondary biomass conversion process according to any one of claims 1 to 4, wherein the CO content of the CO-containing gas is not less than 15%, preferably not less than 50%, most preferably not less than 90% by volume.

6. The secondary biomass conversion process according to claim 5, wherein the CO-containing gas is CO and H₂Mixed gas or synthesis gas.

7. The secondary biomass conversion process according to any one of claims 1 to 6, wherein the desulfurization waste agent of the ferrite compound is a waste agent of a desulfurizing agent using iron oxide as an active component, and Fe is used as the waste agent_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,

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

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

9. The secondary biomass conversion process according to 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;

the FeOOH is at least one of α -FeOOH, β -FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.

10. The secondary biomass conversion process according to any one of claims 1 to 9, wherein the regenerated product of spent desulfurization agent of ferrite compound is a regenerated product obtained by oxidizing, sulfurizing and oxidizing spent desulfurization agent of ferrite compound by slurry method.

11. The secondary biomass conversion process according to claim 10, wherein the regeneration method of spent desulfurization agents of ferrite compounds 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.

12. The secondary biomass conversion process according to any one of claims 1 to 11, wherein the iron-based catalyst has an average particle size of 0.1 μm to 5mm, preferably 5 μm to 100 μm, most preferably 5 to 50 μm.

13. The secondary biomass conversion process according to any one of claims 1 to 12, wherein the volume ratio of pure CO or CO-containing gas to aqueous slurry is (50-10000):1, preferably (100-: 1.

14. the secondary biomass conversion process according to any one of claims 1 to 13, further comprising the step of adding the iron-based catalyst and/or hydrogenation catalyst to the conversion product.

15. The secondary biomass conversion process according to any one of claims 1 to 14, wherein the reaction pressure of the primary conversion reaction and the reaction pressure of the secondary conversion reaction are both 5 to 22MPa, and the reaction temperature is both 100 ℃ and 470 ℃.

16. The secondary biomass conversion process according to any one of claims 1 to 15, wherein the reaction temperature of the primary conversion reaction is 100-400 ℃ and the reaction temperature of the secondary conversion reaction is 300-470 ℃.

17. The secondary biomass conversion process according to any one of claims 1 to 16, wherein the reaction time of the primary conversion reaction is not less than 15min, preferably 15 to 120min, more preferably 15 to 60 min;

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

18. The secondary biomass conversion process according to any one of claims 1 to 17, wherein the aqueous slurry is mixed with pure CO or a 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 50-600 ℃, introducing into a reaction system, and carrying out conversion reaction with water-containing slurry entering the reaction system.

19. The secondary biomass conversion process according to any one of claims 1 to 17, wherein the aqueous slurry is mixed with pure CO or a CO-containing gas to perform a primary conversion reaction, comprising the steps of:

pressurizing partial pure CO or CO-containing gas to 5-22MPa, heating to 50-600 ℃, introducing into the water-containing slurry, and allowing the water-containing slurry to enter a reaction system along with the water-containing slurry to perform a conversion reaction;

the rest part is pressurized to 5-22MPa and heated to 600 ℃ of 300-.

20. An organic matter conversion process according to any one of claims 1 to 19, wherein the true density of the compression moulded material is in the range of 0.75 to 1.5kg/m³In the meantime.

21. The secondary biomass conversion process according to any one of claims 1 to 20, wherein in the compression step, the compression pressure is 0.5 to 5MPa and the compression temperature is 30 to 60 ℃.

22. The secondary biomass conversion process according to any one of claims 1 to 21, wherein the time for the grinding and pulping is 8 to 20 minutes.

23. The secondary biomass conversion process according to any one of claims 1 to 22, wherein the biomass is one or more of crop straw, wood chips, oil residue, leaves, or algae;

the oil is one or more of illegal cooking oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, wash oil, wax oil and anthracene oil.

24. The secondary biomass conversion process according to any one of claims 14 to 23, wherein the hydrogenation catalyst comprises a carrier and an active ingredient supported thereon, wherein the loading of the active ingredient is 0.5 to 15% based on the total weight of the hydrogenation catalyst.

25. The secondary biomass conversion process according to claim 24, wherein the active ingredient 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.

26. The secondary biomass conversion process according to any one of claims 1 to 25, further comprising the step of separating the converted products and collecting the light oil and the heavy oil respectively after the primary conversion reaction and before the secondary conversion reaction.

27. The secondary biomass conversion process according to any one of claims 1 to 26, wherein the reaction system is carried out in a reactor, the reactor being any one of a suspended bed reactor, a slurry bed reactor, a bubbling bed reactor, an ebullating bed reactor, a single-pot 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.

Technical Field

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

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

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

compression: compressing and molding the crushed biomass;

and (3) secondary crushing: crushing the compressed and molded biomass again to obtain biomass powder with the particle size of 80-120 meshes;

mixing biomass powder with oil and water, wherein the biomass powder accounts for 10-60% of the mixed mass, and the water accounts for 0.1-10% of the biomass powder, and grinding and pulping to obtain aqueous slurry;

adding an iron-based catalyst in any one of the steps;

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

mixing the converted product with hydrogen to perform a secondary conversion reaction to prepare an oil product;

the iron-based catalyst is at least one of ferrite compounds, waste desulfurization agents of the ferrite compounds or regenerated substances of the waste desulfurization agents of the iron oxide compounds; and controlling the molar ratio of the iron element to the sulfur element in the reaction system to be 1 (0.5-5).

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).

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

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

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

The CO-containing gas is CO and H₂Mixed gas or synthesis gas.

The waste desulfurizing agent of ferrite compound is waste desulfurizing agent of desulfurizing agent using iron oxide as active component, and uses 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_21.333O₃₂At least one of a regenerated product of a spent devulcanizing agent which is an active component and FeOOH.

The ferric oxide is ferric oxide and/or ferroferric oxide.

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 α -FeOOH, β -FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.

The regenerated product of the desulfurization waste agent of the ferrite compound is obtained by oxidizing, vulcanizing and oxidizing the desulfurization waste agent of the ferrite compound by a slurry method.

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.

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.

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

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

The reaction pressure of the first-order conversion reaction is 5-22MPa, and the reaction temperature is 100-;

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

The reaction temperature of the first-stage conversion reaction is 100-400 ℃, and the reaction temperature of the second-stage conversion reaction is 300-470 ℃.

The reaction time of the first-stage 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.

Mixing the water-containing slurry with pure CO or CO-containing gas to perform primary conversion reaction, and comprising the following steps:

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

Mixing the water-containing slurry with pure CO or CO-containing gas to perform primary conversion reaction, and comprising the following steps:

pressurizing partial pure CO or CO-containing gas to 5-22MPa, heating to 50-600 ℃, introducing into the water-containing slurry, and allowing the water-containing slurry to enter a reaction system along with the water-containing slurry to perform a conversion reaction;

the rest part is pressurized to 5-22MPa and heated to 600 ℃ of 300-.

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

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

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

The grinding and pulping time is 8-20 minutes.

The biomass is one or more of crop straws, sawdust, oil residue, leaves or algae;

the oil is one or more of illegal cooking oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, wash oil, wax oil and anthracene oil.

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

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.

After the first-stage conversion reaction and before the second-stage 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.

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 fluidized 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.

The technical scheme of the invention has the following advantages:

1. the biomass secondary conversion process provided by the invention adopts at least one of ferrite compounds, waste desulfurization agents of ferrite compounds or regenerated products of the waste desulfurization agents of iron oxide compounds as an iron catalyst, adopts aqueous slurry, and simultaneously controls the molar ratio of iron elements to sulfur elements in a reaction system, finds that the free radical polycondensation of biomass in the cracking process can be effectively blocked by carbonylation in the presence of CO, and the conversion active hydrogen hydrogenation of CO and water is realized.

Simultaneously adopts two conversion reactions, and can meet the requirements of different materials with different properties and different products on temperatureAnd different means and parameters such as pressure, atmosphere, heat supply mode, cooling mode, intermediate material separation and the like are flexibly adjusted. 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 gas of the preceding stage conversion reaction is pure CO or gas containing CO, the gas of the subsequent stage conversion reaction is hydrogen, and 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 separately carrying out the secondary conversion reaction are that the reaction temperature is the same or different, the reaction pressure can be the same or different, and the catalysts provided can be the same or different, thus greatly improving the flexibility of operation.

When preparing biomass slurry, crushing the collected biomass to the particle size of 0.2-1 micron, then compressing and molding, and crushing again to obtain biomass powder with the particle size of 80-120 meshes; and then mixing the biomass powder with oil and water, grinding and pulping, and adding an iron catalyst in any step to obtain biomass slurry. When the slurry is prepared, the biomass does not need to be dried, so that the energy consumption is reduced; through the matching of the steps, especially the control of the granularity in the two crushing steps and the control of the compression and grinding pulping steps, the biomass material particles can be mechanically embedded 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, and a large amount of air in the pores is expelled, so that the pulping is facilitated. When the biomass content of the slurry is increased, the slurry is low in viscosity, good in flowability and convenient to convey, the feeding requirement of a subsequent treatment process can be met, and the utilization efficiency of the device is improved.

The preparation method of the slurry provided by the invention has the advantages of simple process, no need of additional additives, saving of the use amount of the oily flowing medium, economy and environmental protection. By matching with the secondary conversion process route provided by the invention, the water in the biomass slurry can generate in-situ hydrogen production reaction, and compared with water, hydrogen is more soluble in oil, and the generated hydrogen is soluble in oil, so that the biomass can be promoted to contact with the hydrogen for reaction, and the reaction performance of the biomass is improved; in addition, the gas in the pore canal of the solid biomass particles is completely soaked by the 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.

2. According to the biomass secondary conversion process provided by the invention, the reaction temperature of the primary conversion reaction is 100-400 ℃, the reaction temperature of the secondary conversion reaction is 300-470 ℃, the primary conversion reaction is mild, carbonylation, cracking and the like are mainly performed, the secondary conversion reaction is severe, and the conversion effect of organic matters is improved.

When the biomass slurry is prepared, the viscosity of the slurry can be further adjusted by controlling parameters such as the temperature and the pressure of raw material compression, the granularity of regrinding and the like. Improve compression pressure and temperature, can destroy material internal pore structure more thoroughly, make to combine more closely between the material, the control of crushing granularity again of cooperation simultaneously for solid-liquid combines better, further reduces the viscosity of thick liquid, increases the holistic mobility of thick liquid.

3. The biomass secondary conversion 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_21.333O₃₂At least one of a regenerated product of a waste desulfurizer containing FeOOH as an active component and a regenerated product of a waste desulfurizer containing FeOOH as an active component is mixed with a proper amount of sulfur by using the above-mentioned catalysts, and it is found that these catalysts are first combined with CO in a CO atmosphere to form a carbonyl compound, and then a carbon atom is bonded to the carbonyl compoundBranches are on small molecular active sites formed after organic matter (such as biomass and the like) is thermally cracked, 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, so that the oxygen content of an oil product is reduced, and the liquefaction yield of solid organic matter and the yield of the oil product transformed from long molecular chains 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 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 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.

4. According to the biomass secondary conversion 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 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

5. According to the biomass secondary 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 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.