CN110747001A - Secondary biomass conversion process - Google Patents

Abstract

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.

Description

Secondary biomass conversion process

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.

Example 1

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

preparing biomass slurry:

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

compressing the crushed straws by a plodder under the compression pressure of 2.5MPa and the compression temperature of 45 ℃ until the true density is 1.0kg/m³；

Crushing the compressed and molded straws again by using a jet mill, sieving the crushed straws with a 100-mesh sieve to obtain straw powder, weighing 40kg of straw powder, and mixing the straw powder with a catalyst to obtain mixed powder;

80kg of waste lubricating oil, mixed powder and 4kg of water are mixed, and grinding and pulping are carried out by adopting a colloid mill for 15 minutes to obtain biomass slurry.

The catalyst added into the slurry is an iron catalyst with the content of 5wt percent, and the added catalystIron seriesThe average particle size of the catalyst was 5 μm.

Iron-based catalyst:

iron seriesThe catalyst is a waste agent of the desulfurizer taking FeOOH as an active component, wherein every 30g of the desulfurizer taking FeOOH as an active component contains soluble iron salt Fe (NO)₃)₃·9H₂6g of O, 9g of ferric salt complexing agent triethanolamine and 15g of amorphous iron oxyhydroxide;

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

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

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

first-order conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the mixture is pressurized to 21MPa and heated to 350 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 21MPa and heated to 500 ℃, 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 conversion reaction is controlled to be 20MPa, the reaction temperature is controlled to be 360 ℃, the reaction time is 20min, and CO and H are reacted with each other₂The volume ratio of the mixed gas to the slurry is 3000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

adding a hydrogenation catalyst into a conversion product, wherein the hydrogenation catalyst consists of alumina and MoO loaded on the alumina, the loading amount of the MoO is 5% by the total weight of the hydrogenation catalyst, and the adding amount of the hydrogenation catalyst is 1.5 wt% of the mass of the conversion product;

then H is introduced₂Dividing into two parts, one part of which is pressurized to 21MPa and heated to 350 ℃, then introducing into a pipeline for conveying the conversion product, the other part of which is pressurized to 21MPa and heated to 500 ℃, then injecting into the slurry bed reactor from the inlet of the slurry bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reactions with the conversion product entering the slurry bed reactor, and controlling the reaction pressure of the secondary conversion reaction18MPa, the reaction temperature is 430 ℃, the reaction time is 30min, H₂The volume ratio of the primary oil product to the secondary oil product is 1000: 1, preparing an oil product.

Example 2

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

preparing biomass slurry:

collecting wheat straw with water content of 10-20 wt%, and pulverizing with superfine pulverizer to particle size of 0.2 μm-5 cm;

compressing the crushed straws by a plodder under the compression pressure of 0.5MPa and the compression temperature of 60 ℃ until the true density is 0.75kg/m³；

Crushing the compressed and molded straws again by using a jet mill, and sieving the crushed straws with a 80-mesh sieve to obtain straw powder;

mixing 100kg of washing oil, 100kg of straw powder and 3kg of water, and grinding and pulping by using a colloid mill for 8 minutes to obtain biomass slurry.

The catalyst added into the slurry is an iron-based catalyst with the content of 1 wt%, and the average particle size of the added iron-based catalyst is 10 mu m.

Iron-based catalyst:

the iron catalyst is a waste agent of a desulfurizer taking iron oxide as an active component, wherein, in 53g of the desulfurizer taking iron oxide as the active component, 10g of calcium bicarbonate, 12g of basic copper carbonate and gamma-Fe are added₂O₃18g，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 space velocity of the catalyst passes through the desulfurization layer and is distributed with the desulfurizer in the desulfurization layer at 50 DEG CPerforming raw desulfurization reaction, removing hydrogen sulfide in tail gas, taking out the waste agent of the reacted desulfurizer after the reaction is finished, and cooling to room temperature to obtain the waste agent of the desulfurizer which takes iron oxide as an active component;

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;

first-order conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the mixed solution is pressurized to 17MPa and heated to 300 ℃, then the mixed solution is introduced into a pipeline for conveying the slurry, the rest of the mixed solution is pressurized to 17MPa and heated to 450 ℃, the mixed solution 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 suspension bed reactor, the reaction pressure of the conversion reaction is controlled to be 16MPa, the reaction temperature is 300 ℃, the reaction time is 30min, and CO and H are reacted with each other₂The volume ratio of the mixed gas to the slurry is 2000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

dividing hydrogen into two parts, wherein one part is pressurized to 16MPa and heated to 350 ℃, then introducing the hydrogen into a pipeline for conveying a conversion product, the other part is pressurized to 16MPa and heated to 500 ℃, then injecting the hydrogen into a slurry bed reactor from an inlet of the slurry bed reactor, and 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 390 ℃, the reaction time to be 15min, and the volume ratio of the hydrogen to the conversion product to be 2000: 1, preparing an oil product.

Example 3

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

preparing biomass slurry:

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

compressing pulverized red algae with a tablet machine at 40 deg.C under 3MPa to true density of 0.95kg/m³；

Crushing the red algae after compression molding by using a jet mill again, and sieving the crushed red algae with a 100-mesh sieve to obtain red algae powder;

and (3) mixing 40kg of crushed red algae powder with 50kg of waste engine oil and 4kg of water, and grinding and pulping for 12min to obtain biomass slurry.

The catalyst added into the slurry is an iron-based catalyst with the content of 1 wt%, and the average particle size of the added iron-based catalyst is 10 mu m.

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.

First-order conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the mixed solution is pressurized to 17MPa and heated to 250 ℃, the mixed solution is introduced into a pipeline for conveying the slurry, the rest of the mixed solution is pressurized to 17MPa and heated to 550 ℃, the mixed solution is injected into the fluidized bed reactor from the 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 conversion reaction is controlled to be 16MPa, the reaction temperature is 380 ℃, the reaction time is 35min, and CO and H are reacted with each other₂The volume ratio of the mixed gas to the slurry is 1000: and 1, collecting the 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 hydrogen by 15.4MPa, heating to 380 ℃, injecting the hydrogen 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 450 ℃, the reaction time to be 20min, and the volume ratio of the hydrogen to the conversion product to be 1500: 1, preparing an oil product.

Example 4

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

preparing biomass slurry:

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

compressing the crushed straws by a plodder under the compression pressure of 5MPa and the compression temperature of 30 ℃ until the true density is 1.5kg/m³；

Crushing the compressed and molded straws again by using a jet mill, and sieving the crushed straws with a 120-mesh sieve to obtain straw powder;

mixing the catalyst with 100kg of anthracene oil, then mixing with 40kg of straw powder and 3kg of water, and grinding and pulping by adopting a colloid mill for 20 minutes to obtain biomass slurry.

The catalyst is an iron catalyst, wherein the content of the regenerant of the waste desulfurizer using iron oxide as an active component is 2 wt% of the slurry, and the average particle size of the added regenerant of the waste desulfurizer using iron oxide as an active component is 400 mu m.

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 every 88g of the desulfurizer taking iron oxide as the active component comprises 50g of cubic ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose;

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

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

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

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

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

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

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

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

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

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

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

first-order conversion reaction:

pressurizing synthesis gas (wherein the volume ratio of CO is 20%) to 8.2MPa, heating to 450 ℃, injecting the synthesis gas into the bubbling bed reactor through 4 injection ports on the side wall and the bottom of the bubbling bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the bubbling bed reactor, wherein the reaction pressure of the conversion reaction is controlled to be 8MPa, the reaction temperature is 380 ℃, the reaction time is 60min, and the volume ratio of the synthesis gas to the slurry is 950: 1, collecting a conversion product;

and (3) secondary conversion reaction:

directly pressurizing hydrogen to 18MPa, heating to 500 ℃, injecting the hydrogen into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with a conversion product entering the slurry bed reactor, controlling the reaction pressure of the secondary conversion reaction to be 18MPa, the reaction temperature to be 400 ℃, the reaction time to be 30min, and H₂Volume ratio to conversion product 1000: 1, preparing an oil product.

Example 5

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

preparing biomass slurry:

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

compressing the crushed straws by a plodder under the compression pressure of 2.5MPa and the compression temperature of 45 ℃ until the true density is 1.0kg/m³；

Crushing the compressed and molded straws again by using a jet mill, and sieving the crushed straws with a 100-mesh sieve to obtain straw powder;

mixing the catalyst with 80kg of waste lubricating oil, 20kg of straw powder and 2kg of water, and grinding and pulping by using a colloid mill for 15 minutes to obtain biomass slurry.

The catalyst is iron catalyst with the content of 8 wt%;

iron-based catalyst:

the iron-based catalyst is Fe_21.333O₃₂Regeneration of spent devulcanizing agent as active component, wherein said Fe is present in an amount of 92g per devulcanizing agent_21.333O₃₂Among desulfurizing agents as active components, Fe_21.333O₃₂Is 55g of anatase type Ti0₂22g of bentonite, 15g of bentonite;

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

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

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

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

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

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

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

hydrogenation catalyst:

the hydrogenation catalyst consists of silicon dioxide and MoO and CoO loaded on the silicon dioxide, wherein the loading amount of the MoO is 5 percent, the loading amount of the CoO is 2 percent, and the particle size of the hydrogenation catalyst is 500 mu m;

first-order conversion reaction:

directly pressurizing the synthesis gas to 20MPa, heating to 450 ℃, injecting the synthesis gas into the slurry bed reactor from the inlet of the slurry bed reactor, reacting with the slurry entering the slurry bed reactor, controlling the reaction pressure of the primary 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 to the slurry to be 2000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

preparing the conversion product and the hydrogenation catalyst into aqueous slurry, wherein the content of the iron catalyst in the aqueous slurry is 5 wt%, pressurizing hydrogen by 16MPa, heating to 410 ℃, injecting the hydrogen into the slurry bed reactor from an inlet of the slurry bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reactions with the aqueous slurry entering the slurry bed reactor, wherein the reaction pressure of the secondary conversion reaction is controlled to be 15MPa, the reaction temperature is 400 ℃, the reaction time is 25min, and the volume ratio of the hydrogen to the aqueous slurry is 2000: 1, preparing an oil product.

Example 6

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

preparing biomass slurry:

collecting corn straw and cotton straw 100kg, mixing with catalyst with water content of 5-20 wt%, and pulverizing with superfine pulverizer to particle size of 0.2 μm-5 cm;

compressing the crushed material by a plodder at 4MPa and 40 deg.C until the true density is 0.9kg/m³；

Crushing the compressed and molded mixed material again by using a jet mill, and sieving the crushed mixed material by using a 100-mesh sieve to obtain mixed powder of straws and a catalyst;

mixing 150kg of rancid oil with the mixed powder and 2kg of water, and grinding and pulping by using a colloid mill for 15 minutes to obtain biomass slurry.

The catalyst is an iron catalyst, wherein the content of the regenerant of the waste desulfurizer taking ferric hydroxide as an active component is 0.3 wt% of the slurry, and the average particle size of the added regenerant of the waste desulfurizer taking ferric hydroxide as an active component is 20 mu m.

Iron-based catalyst:

the iron catalyst is a regeneration product of a waste desulfurizer of which the FeOOH is taken as an active component, wherein every 68g of the total mass of the desulfurizer of which the FeOOH is taken as the active component is α -FeOOH 30g, the amorphous FeOOH 20g, the potassium oxide 8g and the adhesive kaolin 10 g;

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

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, 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;

7) adding sulfur: and (3) adding solid sulfur powder into the regenerated substance 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.

First-order conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 80% and H)₂The ratio is 20%)Pressurizing a part of the slurry to 19.5MPa, heating the slurry to 300 ℃, introducing the slurry into a pipeline for conveying the slurry, pressurizing the other part of the slurry to 19.3MPa, heating the slurry to 480 ℃, injecting the slurry into the slurry bed reactor from 3 injection ports on the bottom and the side wall of the slurry bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reaction on the slurry and the slurry entering the slurry bed reactor, controlling the reaction pressure to be 19MPa, the reaction temperature to be 390 ℃, the reaction time to be 20min, and reacting CO and H₂The 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 dividing hydrogen into two parts, wherein one part is pressurized to 20MPa and heated to 380 ℃, then introducing the hydrogen into a pipeline for conveying a conversion product, the other part is pressurized to 20MPa and heated to 480 ℃, then injecting the hydrogen into the slurry bed reactor from the inlet of the slurry bed reactor, and 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 380 ℃, the reaction time to be 30min, and the volume ratio of hydrogen to the conversion product to be 4000: 1, preparing an oil product.

Example 7

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

preparing biomass slurry:

collecting 100kg of peanut oil residue with water content of 5-15 wt%, mixing with catalyst, and pulverizing with superfine pulverizer to particle size of 0.2 μm-5 cm;

compressing the crushed material by a plodder under the compression pressure of 2.5MPa and the compression temperature of 50 ℃ until the true density is 1.2kg/m³；

Crushing the compressed and molded mixed material again by using a jet mill, and sieving the crushed mixed material by using a 100-mesh sieve to obtain mixed powder of the peanut oil residue and the catalyst;

200kg of illegal cooking oil, mixed powder and 8kg of water are mixed, and grinding and pulping are carried out by adopting a colloid mill for 16 minutes to obtain biomass slurry.

The catalyst used in the slurry is an iron catalyst, the content of the iron catalyst is 0.2 wt%, and the average particle size is 2 mu m;

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 12g of cubic ferroferric oxide and amorphous Fe are contained in every 80g of the desulfurizer taking iron oxide as the active component₂O₃24g of amorphous Fe₂O₃.H₂O39 g and NiO are 5 g;

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

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

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

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

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

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

adding sulfur: adding solid sulfur powder into the regenerated substances until the molar ratio of the iron element to the sulfur element is 1:0.9, so as to ensure that the molar ratio of the iron element to the sulfur element in a reaction system is 1: 2;

first-order 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 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 400 ℃, 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; pressurizing the hydrogen by 19MPa, heating to 490 ℃, injecting the hydrogen into the slurry bed reactor from the 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 18MPa, the reaction temperature to be 400 ℃, the reaction time to be 30min, and the volume ratio of the hydrogen to the converted product to be 1000: 1, preparing an oil product.

Example 8

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

preparing biomass slurry:

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 μm-5 cm;

mixing the pulverized peanut oil residue with catalyst, and compression molding with a plodder at a compression pressure of 2.5MPa and a compression temperature of 50 deg.C until the true density is 1.2kg/m³；

Crushing the compressed and molded material again by using a jet mill, and sieving the crushed material by using a 100-mesh sieve to obtain mixed powder of the peanut oil residue and the catalyst;

mixing 400kg of illegal cooking oil, mixed powder and 8kg of water under the negative pressure of 3990Pa, and grinding and pulping by adopting a colloid mill for 16 minutes to obtain biomass slurry.

The catalyst in the slurry is an iron-based catalyst, wherein the content of the waste agent of the desulfurizer taking FeOOH as an active component is 4 wt% of the biomass slurry, and the average particle size of the added waste agent of the desulfurizer taking FeOOH as an active component is 120 mu m.

Iron-based catalyst:

the iron catalyst is a waste desulfurizer using FeOOH as an active component, wherein, in every 100g of the desulfurizer using FeOOH as an active component, 70g of amorphous FeOOH and 70g of Co₂O₃25g and NiO is 5 g;

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

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

first-order 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 380 ℃, 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 hydrogen by 14MPa, heating to 480 ℃, injecting the hydrogen 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 390 ℃, the reaction time to be 30min, and the volume ratio of the hydrogen to the conversion product to be 1500: 1, preparing an oil product.

Example 9

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

preparing biomass slurry:

collecting 100kg red algae with water content of 70-90 wt%, air drying until water content is lower than 20 wt%, and pulverizing to particle size of 0.2 μm-5 cm;

compressing pulverized red algae with a tablet machine at 40 deg.C under 3MPa to true density of 0.95kg/m³；

Mixing the red algae subjected to compression molding with a catalyst, performing secondary crushing treatment by using a jet mill, and sieving with a 100-mesh sieve to obtain mixed powder of the red algae and the catalyst;

and mixing the crushed mixed powder, 90kg of waste engine oil and 5kg of water under the negative pressure of 133Pa, and grinding and pulping for 12min to obtain biomass slurry.

The catalyst is an iron catalyst, wherein the content of the desulfurizer taking FeOOH as an active component is 8 wt% of the slurry, and the average particle size of the added desulfurizer taking FeOOH as an active component is 300 mu m.

Iron-based catalyst:

the iron-based catalyst adopts a desulfurizer taking FeOOH as an active component, wherein the content of amorphous FeOOH in the desulfurizer taking FeOOH as the active component is 60%, the content of carrier kieselguhr is 30%, and the content of binder cellulose powder is 10% by total mass of the desulfurizer taking FeOOH as the active component;

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

first-order conversion reaction:

reacting CO with H₂The mixed gas (wherein the volume ratio of CO in the mixed gas is 50%) is pressurized to 18MPa, heated to 380 ℃, injected into the slurry bed reactor from 5 injection ports on the bottom and the side wall of the slurry bed reactor, and subjected to cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry bed reactor, the reaction pressure is controlled to be 17MPa, the reaction temperature is 380 ℃, the reaction time is 50min, and the CO and the H are reacted with each other₂The volume ratio of the mixed gas to the slurry is 900: 1, collecting a conversion product;

and (3) secondary conversion reaction:

directly pressurizing hydrogen by 22MPa, heating to 500 ℃, injecting the hydrogen into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with a conversion product entering the slurry bed reactor, controlling the reaction pressure of a secondary conversion reaction to be 22MPa, the reaction temperature to be 430 ℃, the reaction time to be 60min, and the volume ratio of the hydrogen to the conversion product to be 4000: 1, preparing an oil product.

Example 10

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

preparing biomass slurry:

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

compressing the crushed straws by a plodder under the compression pressure of 2.5MPa and the compression temperature of 45 ℃ until the true density is 1.0kg/m³；

Crushing the compressed and molded straws again by using a jet mill, and sieving the crushed straws with a 100-mesh sieve to obtain straw powder;

80kg of waste lubricating oil, 100kg of straw powder, a catalyst and 8kg of water are mixed, and grinding and pulping are carried out by a colloid mill for 15 minutes to obtain biomass slurry.

The adopted catalyst is an iron-based catalyst, the content of the iron-based catalyst is 10 wt% of the biomass slurry, and the average grain size of the added iron-based catalyst is 5 mm.

Iron series catalystAgent:

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 α -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 material₄And (3) extracting the solid material obtained after the extraction and filtration for three times, combining the extraction liquid, recovering the solvent by using a distillation method, simultaneously obtaining the crystallized elemental sulfur, and mixing the residual solid after the extraction liquid is separated with adhesive sesbania powder to obtain the regenerated product of the desulfurizer waste agent, wherein the using amount of the adhesive sesbania powder is 5% of the mass of the solid.

Adding carbon disulfide: adding carbon disulfide into the 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;

first-order conversion reaction:

reacting CO with H₂Mixed gas (CO accounts for 60% and H)₂40 percent) of the slurry is pressurized to 16.8MPa and heated to 250 ℃, and then the slurry is pumped and conveyedIn the liquid pipeline, the rest part is pressurized to 16.2MPa and heated to 550 ℃, then is injected into the fluidized bed reactor from the inlet of the fluidized bed reactor, and carries out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the fluidized bed reactor, the reaction pressure of the conversion reaction is controlled to be 16MPa, the reaction temperature is controlled to be 390 ℃, the reaction time is 60min, and the CO and the H are reacted₂The volume ratio of the mixed gas to the slurry is 5000: 1, collecting a conversion product;

and (3) secondary conversion reaction:

directly pressurizing hydrogen to 19MPa, heating to 410 ℃, injecting the hydrogen into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with a 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.

Comparative example 1

This comparative example provides a co-conversion process of biomass and anthracene oil, the conversion process being the same as in example 4, except that: in the comparative example, the wheat straw and the peanut straw are taken as biomass solids, and the water content of the biomass is 80ppm based on the total weight of the biomass; the molar ratio of the iron element to the sulfur element in the reaction system is 1: 0.1.

Test example 1

The distributions of the products prepared using the processes of examples 1-10 of the present invention were compared to comparative example 1 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;

hydrogen consumption rate (mol/100g solid organic matter slurry mass) — (hydrogen addition mole number-hydrogen mole number in product gas)/solid organic matter slurry mass × 100%;

carbon monoxide consumption rate (mol/100g solid organic matter slurry mass) — (number of moles of carbon monoxide added-number of moles of carbon monoxide in product gas)/number of moles of solid organic matter slurry added × 100%.

The corresponding test results are shown in table 1:

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

Claims (27)

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.