CN108079992B

CN108079992B - Preparation method and application of combined catalyst

Info

Publication number: CN108079992B
Application number: CN201611049034.5A
Authority: CN
Inventors: 林科; 李林; 郭立新; 崔永君; 江莉龙
Original assignee: Beijing Huashi United Energy Technology and Development Co Ltd
Current assignee: Beijing Huashi United Energy Technology and Development Co Ltd
Priority date: 2016-11-21
Filing date: 2016-11-21
Publication date: 2020-07-14
Anticipated expiration: 2036-11-21
Also published as: CN108079992A

Abstract

The invention relates to the field of catalysts, in particular to a preparation method and application of a combined catalyst. The preparation method of the combined catalyst provided by the invention comprises the following steps: carrying out sulfonation treatment on the dry-distilled biomass carbon to obtain a first biomass carbon carrier, and loading a first active component on the first biomass carbon carrier to obtain a hydrolysis hydrogenation catalyst; and (3) acidifying or alkalizing the dry distillation biomass carbon to obtain a second biomass carbon carrier, and mixing and grinding a second active component and the second biomass carbon carrier to obtain the cracking hydrogenation catalyst. The preparation method has the advantages of simple process, short period, low cost, high catalytic activity, no three wastes, effective inhibition of coking phenomenon in the reaction process, improvement of oil products, wide application in the liquefaction process of biomass slurry bed and biomass suspension bed, broadening of the application field of biomass, easy recovery of the catalyst and recycling.

Description

Preparation method and application of combined catalyst

Technical Field

The invention belongs to the field of catalysts, and particularly relates to a preparation method and application of a combined catalyst.

Background

With the continuous expansion of industrial production scale, the demand of energy sources continuously rises, and the supply of non-renewable energy sources such as coal, petroleum, natural gas and the like is seriously insufficient; in addition, the global environment is also severely affected by the massive use of fossil energy. Therefore, the development and utilization of renewable biomass resources have become a global focus.

The global biomass reserves are rich, the biomass reserves are clean renewable resources, the renewable biomass resources are developed and utilized to replace non-renewable resources, and the biomass reserves are an effective way for solving the problem of the deficiency of the non-renewable resources. The biomass oil obtained by pyrolyzing biomass is a mixture of moisture and complex oxygen-containing organic matters, almost comprises all kinds of oxygen-containing organic matters, has higher oxygen content and more complex composition compared with petroleum, and has higher octane value after being upgraded.

At present, the development of a high-selectivity hydrolysis, hydrogenation and cracking catalyst becomes a main driving force for promoting biomass energy sources to produce biomass fuel oil, and is one of important ways for improving the practical maximum production of high-quality biomass fuel oil and chemical raw materials. Therefore, how to improve the catalytic activity of the hydrolytic hydrocracking catalyst and improve the conversion efficiency of biomass becomes an important factor for restricting the continuous development of biomass energy.

In the catalyst structure, the carrier is an important component of the catalyst, not only provides a dispersing place for the metal active component, but also participates in the reaction, and is cooperated with other active components to complete the whole catalytic reaction. Most supports are products of the catalyst industry, commonly used are alumina, silica gel, activated carbon, and certain natural products such as pumice, diatomaceous earth, and the like. The activated carbon material has good adsorbability and certain catalytic performance, so that the activated carbon material loaded with active components is a hot point of research when being applied to a biomass hydrolysis hydrocracking process.

However, most of the activated carbon carrier materials adopted in the prior art are wood activated carbon, shell activated carbon and the like, and the activated carbon has poor strength and poor surface property modulation, so that the application of the activated carbon in the hydrocracking process is limited. In addition, the preparation process of the catalyst taking the activated carbon as the carrier is complex, the distribution of active components on the catalyst carrier is uneven, the hydrolysis degree of the biomass is poor, and the conversion rate of the biomass and the yield of liquefied products are low.

Disclosure of Invention

The technical problems to be solved by the invention are that the existing preparation method of the catalyst taking the active carbon as the carrier has complex process, uneven active component load and lower catalytic activity, and further provides a preparation process of the combined catalyst with simple process, high catalytic activity and environmental friendliness.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the invention provides a preparation method of a combined catalyst, which comprises the following steps:

(1) preparing a first biomass carbon carrier after sulfonation treatment of the dry distillation biomass carbon;

(2) loading a first active component on the first biomass carbon carrier to prepare a hydrolysis hydrogenation catalyst;

(3) acidifying or alkalizing the dry-distilled biomass charcoal to prepare a second biomass charcoal carrier;

(4) and mixing and grinding a second active component and the second biomass charcoal carrier to prepare the cracking hydrogenation catalyst.

Optionally, the sulfonating agent in the sulfonation treatment is concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid; the volume ratio of the dry-distilled biomass charcoal to the sulfonating agent is 1: 5-1: 15, the sulfonation temperature is 120-160 ℃, and the sulfonation time is 1-10 h; h in the acidified acidic medium⁺The mass concentration of the substances is 0.5 mol/L-5 mol/L, the volume ratio of the dry distillation biomass carbon to the acidic medium is 1: 5-1: 15, the acidification temperature is 30-80 ℃, the acidification time is 1-10 h, the mass concentration of OH substances in the alkaline medium subjected to alkalization is 0.5 mol/L-5 mol/L, the volume ratio of the dry distillation biomass carbon to the alkaline medium is 1: 5-1: 15, the alkalization temperature is 30-80 ℃, and the alkalization time is 1-10 h.

Optionally, the sulfonation treatment, the acidification treatment or the alkalization treatment further comprises a distilled water washing step, and the biomass charcoal carrier is washed to be neutral; the washing step is followed by a drying step, and the water content of the dried biomass charcoal carrier is 5-10%.

Optionally, the first active component is ferric salt and/or ferrous salt, and the first active component accounts for 10-50% of the mass of the first biomass carbon carrier by the mass of iron element; the second active component is at least one of oxides of Mo and W in a VIB group and/or oxides of Fe, Co and Ni in a VIII group, and the second active component accounts for 1-5% of the mass of the second biomass charcoal carrier.

Optionally, the step of loading the first active component on the first biomass carbon carrier comprises: mixing the first biomass carbon carrier and the first active component aqueous solution to prepare a suspension, adding a precipitator to precipitate the first active component on the first biomass carbon carrier, and washing and drying to prepare the hydrolysis hydrogenation catalyst; the precipitant is ammonia water or at least one aqueous solution of carbonate, bicarbonate and hydroxide of alkali metal, the temperature in the precipitation process is controlled to be 30-90 ℃, and the pH value is 7-9.

Optionally, the step of mixing and grinding the second active component and the second biomass charcoal carrier comprises: and carrying out vibration grinding and/or plane grinding and/or ball milling on the second active component and the second biomass carbon carrier to obtain the cracking hydrogenation catalyst with the particle size of 0.5-2.5 microns.

Optionally, the specific surface of the biomass charcoal carrier is 50m²/g～200m²Per g, the pore diameter is 1nm to 20nm, and the pore volume is 0.01cm³/g～0.1cm³/g。

The combined catalyst is applied to the hydrogenation reaction of the biomass slurry bed/suspension bed: the hydrolysis hydrogenation catalyst is used for biomass hydrolysis hydrogenation, and the cracking hydrogenation catalyst is added with a vulcanizing agent for cracking hydrogenation.

Optionally, the hydrolysis hydrogenation catalyst and a solvent are prepared into a first suspension, and the mass of the hydrolysis catalyst is 30-40% of that of the first suspension; the cracking hydrogenation catalyst and a solvent are prepared into a second suspension, and the mass of the cracking hydrogenation catalyst is 30-40% of that of the second suspension; the solvent is at least one of vegetable oil, animal oil, coal tar or petroleum.

Optionally, the first suspension and the second suspension are respectively mixed with biomass and then enter a reactor for reaction, wherein the biomass is one or more of straws, reeds, barks and algae of crops and economic crops; the adding amount of the hydrolysis hydrogenation catalyst and the cracking hydrogenation catalyst in the reactor is 0.1-10% of the mass of the raw materials.

The technical scheme of the invention has the following advantages:

1. the embodiment of the invention provides a preparation method of a combined catalyst, which comprises the following steps: (1) performing sulfonation treatment on the dry-distilled biomass carbon to obtain a first biomass carbon carrier; (2) loading a first active component on the first biomass carbon carrier to prepare a hydrolysis hydrogenation catalyst; (3) acidifying or alkalizing the dry-distilled biomass charcoal to obtain a second biomass charcoal carrier; (4) and mixing and grinding the second biomass charcoal carrier and the second active component to prepare the hydrocracking catalyst. The combined catalyst has simple preparation process, short preparation period, low equipment investment and easy scale-up production; the hydrocracking catalyst is prepared by adopting a solid-solid method, the problem of three-waste treatment is avoided in the process, and the method is environment-friendly; meanwhile, the catalyst prepared by the process has uniform active component loading and high catalytic activity, and can be applied to catalytic reactions of various fluidized reaction beds.

2. The embodiment of the invention provides a combined catalyst, which takes biomass charcoal as a carrier, can utilize biomass resources to the maximum extent, and simultaneously takes biomass as renewable resources, is not limited by mineral resources and has low cost; the biomass carbon carrier is sulfonated, so that the biomass hydrolysis can be promoted, and the biomass conversion rate and the yield of liquefied products are improved; meanwhile, the catalyst has the functions of hydrolytic hydrogenation and cracking hydrogenation, and has the advantages of mild reaction conditions, low gas yield, high biomass conversion rate and high biomass fuel oil yield; the active components have the functions of activating hydrogenation and deoxidation, effectively inhibit the coking phenomenon in the reaction process and improve the oil quality.

3. The embodiment of the invention provides the application of the combined catalyst, can be widely applied to the liquefaction process of a biomass slurry bed and a biomass suspension bed, widens the application field of biomass, is easy to recover by the catalyst, and can be recycled.

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. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Example 1

The preparation method of the combined catalyst described in this example includes the following steps:

(1) selecting concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid as a sulfonating agent, treating the biomass carbon at the temperature of 120-160 ℃ for 1-10 h with the volume ratio of the biomass carbon to the sulfonating agent being 1: 5-1: 15;

washing the sulfonated biomass carbon with distilled water to be neutral and drying the sulfonated biomass carbon at the drying temperature of 60-120 ℃ for 2-12 h to obtain the sulfonated biomass carbon with the water content of 5-10 percent and the specific surface area of 50m²/g～200m²G, the aperture is 1 nm-20 nm, and the pore volume is 0.01cm³/g～0.1cm³A first biomass charcoal carrier per gram.

In the embodiment of the invention, concentrated sulfuric acid is used as a sulfonating agent, the sulfonation is carried out at 160 ℃ for 10h according to the volume ratio of the biomass charcoal to the sulfonating agent of 1:15, then distilled water is used for washing to be neutral, dehydration is carried out, and drying is carried out for 8 hours at 100 ℃ to obtain the product with the water content of 8% and the specific surface area of 200m²G, pore diameter of 20nm and pore volume of 0.1cm³A first biomass charcoal carrier per gram.

(2) Preparing a first active component, namely one of ferric salt and/or ferrous salt, into an aqueous solution with the mass fraction of 20% -50%, and mixing the aqueous solution with the first biomass carbon carrier in the step (1) to form a suspension, wherein the first active component accounts for 10% -50% of the mass of the first biomass carbon carrier in terms of metal elements;

adding aqueous solution of ammonia water or carbonate, bicarbonate and hydroxide of alkali metal, adjusting the pH value of the system to 7-9, and reacting for 1-4 h at the reaction temperature of 30-90 ℃;

and after the reaction is finished, filtering the solid-liquid mixture, washing the solid-liquid mixture for 3 times by using distilled water, drying the solid-liquid mixture at the temperature of between 80 and 120 ℃ until the water content of the hydrolysis hydrogenation catalyst is 5 to 10 percent.

In this example, a 30% ferrous sulfate aqueous solution and a first biomass charcoal carrier were mixed, the ferrous sulfate accounts for 50% of the mass of the first biomass charcoal carrier in terms of iron element, ammonia water was added, the system pH was adjusted to 8, the temperature was controlled to 30 ℃ to 45 ℃, and the reaction was carried out for 2 hours. After the reaction is finished, washing the mixture for 3 times by using distilled water, and drying the mixture at 100 ℃ to obtain the hydrolysis hydrogenation catalyst with the water content of 10 percent.

(3) Choose H⁺Treating the biomass charcoal at the temperature of 30-80 ℃ for 1-10 h by using sulfuric acid or hydrochloric acid or nitric acid solution with the concentration of 0.5 mol/L-5 mol/L and acidic medium according to the volume ratio of 1: 5-1: 15;

washing the acidified biomass charcoal with distilled water to be neutral and drying at 60-120 ℃ for 2-12 h to obtain the biomass charcoal with the water content of 5-10% and the specific surface area of 50m²/g～200m²G, the aperture is 1 nm-20 nm, and the pore volume is 0.01cm³/g～0.1cm³A second biomass charcoal carrier per gram.

As an embodiment of the invention, in the embodiment, according to the volume ratio of the biomass charcoal to 5 mol/L hydrochloric acid of 1:5, acidification treatment is carried out for 10 hours at the temperature of 80 ℃, then distilled water is used for washing to be neutral, dehydration is carried out, drying is carried out for 8 hours at the temperature of 100 ℃, and the water content is 7 percent, and the specific surface area is 170m²G, pore diameter of 20nm and pore volume of 0.06cm³A second biomass charcoal carrier per gram.

(4) And carrying out vibration grinding and/or plane grinding and/or ball milling on a second active component and the second biomass carbon carrier to obtain the cracking hydrogenation catalyst with the particle size of 0.5-2.5 microns.

The second active component is one or more of Mo and W oxides in a VIB group, or one or more of Fe, Co and Ni oxides in a VIII group; the active component of the catalyst accounts for 1-5% of the second biomass carbon carrier by mass of metal elements, and the cracking hydrogenation catalyst with the particle size of 0.5-2.5 μm is obtained after vibration grinding and/or plane grinding and/or ball milling.

In this example, nickel oxide and molybdenum oxide were mixed with the second biomass charcoal support and ground in a ball mill to obtain a 0.5 to 1.0 μm cracking/hydrogenation catalyst. Calculated by metal elements, the nickel oxide and the molybdenum oxide account for 3% of the mass of the second biomass charcoal carrier.

The embodiment also provides an application of the catalyst prepared by the method in a biomass slurry/suspension bed hydrogenation process, and the specific application mode is as follows:

preparing a hydrolysis hydrogenation catalyst and vegetable oil into a first suspension, wherein the hydrolysis hydrogenation catalyst accounts for 40% of the mass of the first suspension; and preparing a second suspension from the cracking hydrogenation catalyst and the vegetable oil, wherein the cracking hydrogenation catalyst accounts for 30% of the mass of the second suspension.

Adding the first suspension to perform hydrolysis hydrogenation on the biomass, wherein the hydrolysis hydrogenation catalyst accounts for 8% of the mass of the raw material biomass corn straw, the temperature is 350-400 ℃, the pressure is 13-15 MPa, and the reaction time is 30-40 min.

And adding a second suspension and a vulcanizing agent to carry out cracking hydrogenation on the biomass, wherein the cracking hydrogenation catalyst accounts for 10% of the mass of the raw material biomass corn straw, the vulcanizing agent accounts for 1% of the mass of the raw material biomass, the temperature is 430-450 ℃, the pressure is 20-22 MPa, and the reaction time is 30-40 min.

The total reaction biomass conversion was 98.4% and the liquor yield was 69.6%.

Example 2

(1) selecting chlorosulfonic acid as sulfonating agent, sulfonating at 120 deg.C for 7 hr according to the volume ratio of biomass charcoal to sulfonating agent of 1: 12, washing with distilled water to neutrality, dehydrating, and drying at 120 deg.C for 12 hr to obtain product with water content of 5% and specific surface area of 120m²G, pore diameter of 1nm and pore volume of 0.06cm³A first biomass charcoal carrier per gram.

(2) Mixing a 50% ferrous chloride aqueous solution and a first biomass carbon carrier, wherein ferrous chloride accounts for 30% of the mass of the first biomass carbon carrier in terms of iron element, adding ammonia water, adjusting the pH value of the system to 9, controlling the temperature to be 45-60 ℃, and reacting for 3 hours. After the reaction is finished, washing the reaction product for 3 times by using distilled water, and drying the reaction product at 110 ℃ to obtain the hydrolysis hydrogenation catalyst with the water content of 7 percent.

(3) Alkalizing the biomass charcoal and 0.5 mol/L sodium hydroxide solution at the temperature of 50 ℃ for 6 hours according to the volume ratio of the biomass charcoal to the 0.5 mol/L sodium hydroxide solution of 1:15, then washing the biomass charcoal to be neutral by using distilled water, dehydrating the biomass charcoal and drying the biomass charcoal at the temperature of 80 ℃ for 6 hours to obtain a second biomass charcoal carrier with the water content of 6 percent.

(4) And mixing the tungsten oxide with a second biomass charcoal carrier, and grinding in a vibration grinder to obtain the cracking hydrogenation catalyst with the particle size of 1.0-1.5 microns. And the tungsten oxide accounts for 5% of the mass of the second biomass charcoal carrier in terms of metal elements.

preparing a hydrolysis hydrogenation catalyst and coal tar into a first suspension, wherein the hydrolysis hydrogenation catalyst accounts for 35% of the mass of the first suspension; and preparing a second suspension from the cracking hydrogenation catalyst and coal tar, wherein the cracking hydrogenation catalyst accounts for 40% of the mass of the second suspension.

Adding the first suspension to perform hydrolysis hydrogenation on the biomass, wherein the hydrolysis hydrogenation catalyst accounts for 10% of the bark mass of the biomass as the raw material, the temperature is 300-350 ℃, the pressure is 8-10 MPa, and the reaction time is 50-60 min.

And adding a second suspension and a vulcanizing agent to carry out cracking hydrogenation on the biomass, wherein the cracking hydrogenation catalyst accounts for 7% of the mass of the bark of the raw material biomass, the vulcanizing agent accounts for 0.5% of the mass of the bark of the raw material biomass, the temperature is 380-400 ℃, the pressure is 15-17 MPa, and the reaction time is 50-60 min.

The total reaction biomass conversion was 96.6% and the liquor yield was 62.7%.

Example 3

(1) selecting fuming sulfuric acid as a sulfonating agent, sulfonating for 1h at 135 ℃ according to the volume ratio of the biomass carbon to the sulfonating agent of 1:5, then washing the sulfonated biomass carbon and the sulfonating agent to be neutral by using distilled water, dehydrating, and drying for 2h at 60 ℃ to obtain a first biomass carbon carrier with the water content of 7%.

(2) Mixing ferric chloride with the mass fraction of 40% with a first biomass carbon carrier, wherein the ferric chloride accounts for 10% of the mass of the first biomass carbon carrier in terms of iron element, adding ammonia water, adjusting the pH value of the system to 7, controlling the temperature to be 75-90 ℃, and reacting for 1 h. After the reaction, washing the mixture for 3 times by using distilled water, and drying the mixture at 120 ℃ to obtain the hydrolysis hydrogenation catalyst with the water content of 9 percent.

(3) Alkalizing the biomass charcoal and 2.5 mol/L potassium hydroxide solution at the temperature of 30 ℃ for 4h according to the volume ratio of the biomass charcoal to the 2.5 mol/L potassium hydroxide solution, washing the biomass charcoal to be neutral by using distilled water, dehydrating the biomass charcoal, and drying the biomass charcoal at the temperature of 60 ℃ for 12h to obtain a second biomass charcoal carrier with the water content of 10%.

(4) Mixing the molybdenum oxide with a second biomass carbon carrier, and grinding in a vibration grinder to obtain the cracking hydrogenation catalyst with the particle size of 1.5-2.0 μm. Calculated by metal elements, the molybdenum oxide accounts for 1% of the mass of the second biomass charcoal carrier.

preparing a hydrolysis hydrogenation catalyst and animal oil into a first suspension, wherein the hydrolysis hydrogenation catalyst accounts for 30% of the mass of the first suspension; and preparing a second suspension from the cracking hydrogenation catalyst and the animal oil, wherein the cracking hydrogenation catalyst accounts for 35% of the mass of the second suspension.

And adding the first suspension to perform hydrolysis hydrogenation on the biomass, wherein the hydrolysis hydrogenation catalyst accounts for 4% of the mass of the raw material biomass reed, the temperature is 200-250 ℃, the pressure is 10-12 MPa, and the reaction time is 40-50 min.

And adding a second suspension and a vulcanizing agent to carry out cracking hydrogenation on the biomass, wherein the cracking hydrogenation catalyst accounts for 0.1% of the mass of the original reeds, the vulcanizing agent accounts for 0.8% of the mass of the raw reeds, the temperature is 390-410 ℃, the pressure is 19-21 MPa, and the reaction time is 40-50 min.

The total reaction biomass conversion was 92.6% and the liquor yield was 63.1%.

Example 4

(1) selecting fuming sulfuric acid as a sulfonating agent, sulfonating for 3 hours at the temperature of 140 ℃ according to the volume ratio of the biomass carbon to the sulfonating agent of 1: 8, then washing the sulfonated biomass carbon with distilled water to be neutral, dehydrating, and drying for 4 hours at the temperature of 90 ℃ to obtain a first biomass carbon carrier with the water content of 10%.

(2) Mixing ferric nitrate with the mass fraction of 50% with a first biomass charcoal carrier, wherein the ferric nitrate accounts for 25% of the mass of the first biomass charcoal carrier in terms of iron element, adding ammonia water, adjusting the pH value of the system to 7, controlling the temperature to be 60-75 ℃, and reacting for 4 hours. After the reaction is finished, washing the mixture for 3 times by using distilled water, and drying the mixture at 80 ℃ to obtain the hydrolysis hydrogenation catalyst with the water content of 5 percent.

(3) Acidifying the biomass charcoal and 4.0 mol/L nitric acid solution at a volume ratio of 1: 12 at 60 ℃ for 1h, washing the biomass charcoal with distilled water to be neutral, dehydrating, and drying at 120 ℃ for 2h to obtain a second biomass charcoal carrier with the water content of 10%.

(4) Mixing the cobalt oxide with a second biomass charcoal carrier, and grinding in a plane grinder to obtain the cracking hydrogenation catalyst with the particle size of 2.0-2.5 microns. Calculated by metal elements, the cobalt oxide accounts for 3% of the mass of the second biomass charcoal carrier.

preparing a hydrolysis hydrogenation catalyst and coal tar into a first suspension, wherein the hydrolysis hydrogenation catalyst accounts for 38% of the mass of the first suspension; and preparing a second suspension from the cracking hydrogenation catalyst and coal tar, wherein the cracking hydrogenation catalyst accounts for 30% of the mass of the second suspension.

Adding the first suspension to perform hydrolysis hydrogenation on the biomass, wherein the hydrolysis hydrogenation catalyst accounts for 0.1% of the mass of the raw material biomass algae, the temperature is 250-300 ℃, the pressure is 11-13 MPa, and the reaction time is 45-55 min.

And adding a second suspension and a vulcanizing agent to carry out cracking hydrogenation on the biomass, wherein the cracking hydrogenation catalyst accounts for 2% of the mass of the raw biomass algae, the vulcanizing agent accounts for 2% of the mass of the raw biomass, the temperature is 380-450 ℃, the pressure is 15-22 MPa, and the reaction time is 45-55 min.

The total reaction biomass conversion was 94.0% and the liquor yield was 62.4%.

Comparative example 1

The combined catalyst preparation method described in this comparative example comprises the following steps:

(1) selecting fuming sulfuric acid as sulfonating agent, sulfonating at 160 deg.C for 10 hr according to the volume ratio of biomass carbon to sulfonating agent of 1:15, washing with distilled water to neutrality, dehydrating, drying at 100 deg.C for 8 hr to obtain product with water content of 8% and specific surface of 200m²G, pore diameter of 20nm and pore volume of 0.1cm³A first biomass charcoal carrier per gram.

(2) Mixing a ferrous sulfate aqueous solution with the mass fraction of 30% with a first biomass carbon carrier, wherein ferrous sulfate accounts for 50% of the mass of the first biomass carbon carrier in terms of iron element, adding ammonia water, adjusting the pH value of the system to 8, controlling the temperature to be 30-45 ℃, and reacting for 2 h. After the reaction is finished, washing the mixture for 3 times by using distilled water, and drying the mixture at 100 ℃ to obtain the hydrolysis hydrogenation catalyst with the water content of 10 percent.

(3) Acidifying at 80 deg.C for 10h according to the volume ratio of biomass charcoal and 5 mol/L hydrochloric acid solution of 1:5, washing with distilled water to neutrality, dehydrating, and drying at 100 deg.C for 8h to obtain biomass charcoal with water content of 7% and specific surface area of 170m²G, pore diameter of 20nm and pore volume of 0.06cm³A second biomass charcoal carrier per gram.

(4) Mixing nickel oxide and molybdenum oxide with a second biomass charcoal carrier. Calculated by metal elements, the nickel oxide and the molybdenum oxide account for 3% of the mass of the second biomass charcoal carrier.

The comparative example also provides an application of the catalyst prepared by the method in a biomass slurry/suspension bed hydrogenation process, and the specific application mode is as follows:

And adding a second suspension and a vulcanizing agent to carry out cracking hydrogenation on the biomass, wherein the cracking hydrogenation catalyst accounts for 10% of the mass of the raw material biomass corn straw, the vulcanizing agent accounts for 1% of the mass of the raw material biomass corn straw, the temperature is 430-450 ℃, the pressure is 20-22 MPa, and the reaction time is 30-40 min.

The total reaction biomass conversion was 85.6% and the liquor yield was 56.2%.

Comparative example 2

(3) Acidifying at 80 deg.C for 10h according to the volume ratio of biomass charcoal and 5 mol/L hydrochloric acid solution of 1:5, washing with distilled water to neutrality, dehydrating, and drying at 100 deg.C for 8h to obtain biomass charcoal with water content of 7% and specific surface area of 170m²/g、Pore diameter of 20nm and pore volume of 0.06cm³A second biomass charcoal carrier per gram.

(4) And grinding the nickel oxide, the molybdenum oxide and the second biomass charcoal carrier by using a ball mill respectively to obtain a mixture of the nickel oxide and the molybdenum oxide with the particle size of 1.0-1.5 mu m and a biomass charcoal carrier with the particle size of 0.5-1.0 mu m respectively, and mixing the nickel oxide and the molybdenum oxide with the second biomass charcoal carrier. Calculated by metal elements, the nickel oxide and the molybdenum oxide account for 3% of the mass of the second biomass charcoal carrier.

The total reaction biomass conversion was 90.1%, and the liquor yield was 61.0%.

Comparative example 3

(4) Mixing nickel oxide, molybdenum oxide and a second biomass carbon carrier, and grinding in a ball mill to obtain the cracking hydrogenation catalyst with the particle size of 0.5-1.0 μm. Calculated by metal elements, the nickel oxide and the molybdenum oxide account for 3% of the mass of the second biomass charcoal carrier.

preparing a hydrolysis hydrogenation catalyst and a solvent into a first suspension, wherein the hydrolysis hydrogenation catalyst accounts for 40% of the mass of the first suspension; and preparing a second suspension from the cracking hydrogenation catalyst and a solvent, wherein the cracking hydrogenation catalyst accounts for 30% of the mass of the second suspension.

And adding the second suspension to carry out cracking hydrogenation on the biomass, wherein the cracking hydrogenation catalyst accounts for 10% of the mass of the raw material biomass corn straw, the temperature is 430-450 ℃, the pressure is 20-22 MPa, and the reaction time is 30-40 min.

The total reaction biomass conversion was 58.6% and the liquor yield was 43.7%.

Comparing the reaction yield of examples 1-4 with the total reaction biomass conversion rate and liquid yield of comparative examples 1-3, it can be shown that the catalyst of the present application has uniform active component loading, high catalytic activity due to the addition of a vulcanizing agent during the reaction, mild reaction conditions, low gas yield, effective coking inhibition, and high biomass conversion rate and biomass fuel oil yield.

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

Claims

1. An application of a catalyst used in combination in a biomass slurry bed/suspension bed hydrogenation reaction is characterized in that,

the preparation method of the combined catalyst comprises the following steps:

(1) selecting concentrated sulfuric acid as a sulfonating agent, sulfonating for 10 hours at 160 ℃ according to the volume ratio of the biomass carbon to the sulfonating agent of 1:15, then washing the sulfonated biomass carbon and the sulfonating agent to be neutral by using distilled water, dehydrating, and drying the sulfonated biomass carbon and the sulfonating agent for 8 hours at 100 ℃ to obtain the sulfonated biomass carbon with the water content of 8 percent and the specific surface area of 200m²G, pore diameter of 20nm and pore volume of 0.1cm³A first biomass charcoal carrier per gram;

(2) mixing a 30% ferrous sulfate aqueous solution and a first biomass charcoal carrier, wherein ferrous sulfate accounts for 50% of the mass of the first biomass charcoal carrier in terms of iron element, adding ammonia water, adjusting the pH of the system to be =8, controlling the temperature to be 30-45 ℃, and reacting for 2 hours; after the reaction is finished, washing the mixture for 3 times by using distilled water, and drying the mixture at 100 ℃ to obtain a hydrolysis hydrogenation catalyst with the water content of 10 percent;

(3) acidifying the biomass charcoal and 5 mol/L hydrochloric acid at a volume ratio of 1:5 at 80 deg.C for 10h, washing with distilled water to neutrality, dehydrating, and drying at 100 deg.C for 8h to obtain biomass charcoal with water content of 7% and specific surface area of 170m²G, pore diameter of 20nm and pore volume of 0.06cm³In terms of/gII, biomass charcoal carriers;

(4) mixing nickel oxide, molybdenum oxide and a second biomass carbon carrier, and grinding in a ball mill to obtain a cracking hydrogenation catalyst with the particle size of 0.5-1.0 μm; calculated by metal elements, the nickel oxide and the molybdenum oxide account for 3% of the mass of the second biomass charcoal carrier;

the application mode is as follows:

preparing a hydrolysis hydrogenation catalyst and vegetable oil into a first suspension, wherein the hydrolysis hydrogenation catalyst accounts for 40% of the mass of the first suspension; preparing a second suspension from the cracking hydrogenation catalyst and vegetable oil, wherein the cracking hydrogenation catalyst accounts for 30% of the mass of the second suspension;

adding the first suspension to perform hydrolysis hydrogenation on the biomass, wherein the hydrolysis hydrogenation catalyst accounts for 8% of the mass of the raw material biomass corn straw, the temperature is 350-400 ℃, the pressure is 13-15 MPa, and the reaction time is 30-40 min;