CN110540857A

CN110540857A - Method for preparing chemical raw material and liquid fuel from biomass

Info

Publication number: CN110540857A
Application number: CN201910718024.3A
Authority: CN
Inventors: 曾宿主; 杨发新; 王庆明; 刘玉珍; 刘艳艳
Original assignee: Beijing Lianyi Huahai Energy Technology Co Ltd
Current assignee: Heilongjiang Longyou Petrochemical Co., Ltd
Priority date: 2019-08-05
Filing date: 2019-08-05
Publication date: 2019-12-06
Anticipated expiration: 2039-08-05
Also published as: CN110540857B

Abstract

The invention discloses a method for preparing chemical raw materials and liquid fuel by biomass, which comprises the following steps: performing pyrolysis reaction on a biomass raw material to obtain a pyrolysis product comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke; step two, preparing a first hydrogenation catalyst by taking the obtained pyrolysis semicoke as a carrier for later use; step three, preparing the obtained biological tar, the first hydrogenation catalyst and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing part of the hydrocarbon oil with part of the obtained tail oil to prepare the slurry, and step four, taking the obtained light biological oil as a raw material, and utilizing the second hydrogenation catalyst for fixed bed hydrogenation reaction to obtain the chemical raw material and the liquid fuel. The biomass conversion process provided by the invention is simple in pulping and can be continuously operated.

Description

method for preparing chemical raw material and liquid fuel from biomass

Technical Field

the invention relates to the field of application of biomass materials. In particular to a method for preparing chemical raw materials and liquid fuels by biomass.

background

biomass includes plants, animals, microorganisms and their excretions and metabolites, and is the only material renewable resource. The biomass can be utilized from the perspective of renewable energy sources, and is directly combusted for power generation; however, from the resource utilization point of view, biomass is a precious renewable hydrocarbon resource and can be used as a supplement of petroleum and natural gas to produce chemical raw materials and liquid fuels. The quantity of crop straws generated in China is about 7 hundred million tons every year, forestry wastes are about 2.5 hundred million tons, and if the forestry wastes are partially converted into liquid fuels and chemical raw materials, about 1-2 million tons of petroleum energy can be replaced, so that the external dependence of the petroleum in China can be greatly reduced, and the method has a slight significance on the energy safety war in China.

Pyrolysis is generally adopted in the current biomass oil production. Biomass pyrolysis refers to the conversion of biomass into pyrolysis gas (commonly called "wood gas"), pyrolysis biological tar (commonly called "wood tar"), pyrolysis water (commonly called "wood vinegar"), pyrolysis semicoke (commonly called "charcoal") by thermochemical conversion under the condition of isolating air or supplying a small amount of air, and the like, wherein if the temperature rise rate is more than 1000 ℃/s, the yield of the pyrolysis tar can reach more than 60%. The biological tar produced by the biomass pyrolysis oil production technology is mainly phenol, ketone, aldehyde and alcohol compounds rich in oxygen, has hundreds of compositions, is difficult to separate, is difficult to directly and efficiently separate into chemical products, and can only be sold as low-calorific-value fuel oil. Moreover, the stability of the biological pyrolytic tar is poor, and the biological pyrolytic tar is easy to oxidize, deteriorate and polycondense when stored under natural conditions. Therefore, there is a need for biomass pyrolysis and bio-tar processing technologies to convert biomass into chemical raw materials and high-value liquid fuels that can be directly utilized.

In the prior art, CN103242871B discloses a heavy oil-biomass hydrogenation industrial treatment process, which uses a slurry bed hydrocracking reactor, mixes 40-100 mesh pine sawdust and Craya vacuum distillate with a distillation range of 360-540 ℃ according to a mass ratio of 10% of the pine sawdust to be used as a feed, and converts biomass into liquid bio-oil and coke under the conditions of a catalyst, high temperature and high pressure. However, in the method of co-refining biomass and heavy oil, compared with the conventional method of co-refining coal and heavy oil, the biomass is difficult to pulp and cannot be continuously operated, only 10% of biomass can be added, and the biomass processing efficiency is low. Also, CN108085036A discloses a multistage liquefaction process of biomass, which comprises preparing slurry from biomass, a first catalyst and bio-oil, and reacting at 13-25 MPa and high temperature to obtain a first liquefied product; and then adding a second catalyst slurry oil prepared from a second catalyst and bio-oil into the first liquefied product, and continuing to react at a high temperature of 13-25 MPa to prepare a second liquefied product. The method can convert the biomass into oil products and chemical raw materials, but the biomass pulping is difficult and has high moisture content; the liquefaction reaction condition is harsh, and the pressure is between 13 and 25 MPa; the operation is intermittent operation, which limits the application.

In summary, in the process of converting biomass into chemical raw materials and liquid fuels in the prior art, at least the disadvantages of discontinuous biomass conversion process and difficult biomass pulping exist.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.

the invention also aims to provide a method for preparing chemical raw materials and liquid fuels by using biomass, and the provided biomass conversion process is simple in pulping and can be continuously operated.

to achieve these objects and other advantages in accordance with the present invention, there is provided a method for producing chemical raw materials and liquid fuels from biomass, comprising:

the method comprises the following steps of firstly, carrying out pyrolysis reaction on a biomass raw material, wherein the pyrolysis temperature is set to be 300-800 ℃, and obtaining pyrolysis products comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke;

Step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier for later use;

Step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing part of the obtained tail oil with the hydrocarbon oil to prepare the slurry, and replacing or supplementing the part with the hydrocarbon oil when the quantity of the circulating tail oil is insufficient, so that the mass ratio of the hydrocarbon oil and/or the tail oil, the catalyst and the biological tar is 1: 0.001-0.2: 0.1-5, the operating temperature of the slurry bed is 200-450 ℃, the operating pressure is 2-18 MPa, the volume airspeed is 0.4-10.0h < -1 >, and the volume ratio of the hydrogen to the oil is 100-1000; the distillation separation temperature of the hydrogenated bio-oil is 250-520 ℃;

And step four, taking the light bio-oil obtained in the step three as a raw material, carrying out fixed bed hydrogenation reaction by using a second hydrogenation catalyst, and distilling and separating a product obtained by the hydrogenation reaction to obtain the chemical raw material and the liquid fuel, wherein the operating temperature of the fixed bed reactor is between 200 and 420 ℃, the operating pressure is between 2 and 18MPa, the volume space velocity is between 0.01 and 5.0h < -1 >, and the volume ratio of hydrogen to oil is 200-.

according to the technical scheme, the biomass is converted into the chemical raw materials and the liquid fuel after pyrolysis, slurry bed hydrogenation and fixed bed hydrogenation, so that the continuous operability of the process of converting the biomass into the chemical raw materials and the liquid fuel is realized, and the problem of difficulty in biomass pulping is solved. The slurry bed reaction mode is adopted to treat the biological tar, the long-period operation can be realized, the pressure drop is avoided, the conversion rate is high, and the worst residual oil can be treated.

preferably, the biomass raw material in the first step comprises plants, animals, agricultural and forestry waste, municipal waste and industrial waste.

Preferably, the operating temperature of the fixed bed reactor in the fourth step is between 200 and 420 ℃, the operating pressure is between 2 and 18MPa, the volume space velocity is between 0.01 and 5.0h < -1 >, and the volume ratio of hydrogen to oil is 200-; the second hydrogenation catalyst active component is one or more of metals in VIB group and/or VIII group, including one or more of Co, Mo, Ni, W, Fe, Pt, Pb, Ru, Rh, Os and Ir, wherein the best effect is one or more of Co, Mo, Ni and W; the second catalyst further comprises a carrier, wherein the carrier is one or more of alumina, zeolite molecular sieve, other metal oxide or mixed metal oxide; wherein the mass ratio of the active components of the catalyst to the carrier is 0.01-0.5: 1.

Preferably, the pyrolysis reaction in the first step is carried out in a rotating cone, a rotary kiln, a vertical furnace or a fluidized bed, and the pyrolysis reactor is selected from various types and can realize continuous operation of the whole process.

Preferably, the temperature rise rate of the pyrolysis reaction in the step one is 10-10000 ℃/min.

Preferably, the particle size of the pyrolysis semicoke carrier in the second step is 10-1000 um, and the preparation step of the first hydrogenation catalyst in the second step is as follows: preactivating the pyrolysis semicoke obtained in the step one to obtain the pyrolysis semicoke with the specific surface area of 300-1200 m 2/g; and then, preparing the first hydrogenation catalyst by using the pyrolysis semicoke obtained by pre-activation as a carrier, wherein the active center of the first hydrogenation catalyst is one or more of metals in families VIB and/or VIII, and the active center of the first hydrogenation catalyst comprises one or more of Fe, Co, Mo, Ni or W, and the effect of Fe and/or Mo is optimal. The ratio of the active center to the active pyrolysis semicoke is 0.1-0.6: 1.

Preferably, the hydrocarbon oil in step three includes one or more of animal oil, vegetable oil, chemical oil products produced by the process, straight-run diesel oil, straight-run wax oil, catalytic cracking cycle oil, catalytic cracking diesel oil, catalytic cracking wax oil, coking diesel oil and coking wax oil.

Preferably, the slurry bed hydrogenation reactor in the third step is a bubbling reactor, an airlift sleeve reactor or a forced slurry circulation reactor, and the slurry bed reactors are selected in various ways and can realize continuous operation of the whole process.

Preferably, the other part of tail oil obtained by distillation and separation of the hydrogenated bio-oil in the step three is thrown outwards, wherein the volume ratio of the tail oil for circulation to the tail oil thrown outwards is 0.1-10: 1.

Preferably, in the second step, the pyrolysis semicoke is pre-activated, and the pre-activation step comprises:

step one, putting the pyrolysis semicoke obtained in the step one into an alkaline solution with the mass fraction of 8-12 wt%, continuously raising the temperature of the alkaline solution to 100 ℃ while stirring, and reacting for 2-4 hours, wherein the mass ratio of the pyrolysis semicoke to the alkaline solution is 1: 8-20; then taking out the pyrolysis semicoke, and cleaning the pyrolysis semicoke by using distilled water until the surface pH value is neutral;

Secondly, raising the temperature of the activation furnace to 500-600 ℃, preheating for 10-30 min, introducing carbon dioxide for 5-8 min, wherein the flow rate of the carbon dioxide is 6-8 mL/min; and (3) placing the neutral pyrolysis semicoke obtained in the first step into an activation furnace, raising the temperature in the activation furnace to 800-900 ℃, adjusting the flow rate of carbon dioxide to 10-12 mL/min, and activating for 2-4 h.

In the technical scheme, the alkaline solution in the first step is preferably a KOH solution or a NaOH solution, the pyrolysis semicoke is activated by a two-step activation method, and compared with a traditional one-step method or a simple combination method of an alkaline solution activation method and high-temperature activation, the activated pyrolysis semicoke obtained by the two-step activation method provided by the invention has better catalytic performance of the prepared hydrogenation catalyst.

The invention at least comprises the following beneficial effects: firstly, the biomass conversion process provided by the invention can be operated continuously for a long period; secondly, in the method for preparing chemical raw materials and liquid fuel by using biomass, the biomass pulping process is simple, the operation is easy, and the method can be popularized to a biomass recycling project in a large range; thirdly, in the method for preparing chemical raw materials and liquid fuel by using biomass, the pyrolysis semicoke is used as a carrier for preparing the hydrogenation catalyst, the activation process is innovative, and the obtained catalyst has good catalytic activity.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

drawings

FIG. 1 is a process flow diagram of one embodiment of the present invention.

Detailed Description

The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.

As shown in figure 1, the invention provides a method for preparing chemical raw materials and liquid fuel from biomass, which has simple technical process and can be operated continuously for a long period. The process comprises the following steps:

Example 1

Firstly, straw is used as a biomass raw material, the straw is pre-dried and crushed, and then enters a rotating cone pyrolysis reactor for pyrolysis reaction, the operation temperature of biomass pyrolysis is 500 ℃, the heating rate is 500 ℃/min, and pyrolysis products comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke are obtained; the distribution of the pyrolysis products obtained is shown in table 1. The elemental analysis of the bio-tar is shown in Table 2.

And step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier, grinding the pyrolysis semicoke to 40-200 meshes in advance, and preparing the slurry bed hydrogenation catalyst by taking iron oxyhydroxide as an active component. Wherein the ratio of the active components to the pyrolytic semicoke is 0.5:1 for later use;

and step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing the hydrocarbon oil for preparing the slurry in one part of the obtained tail oil, and swinging the other part of the obtained tail oil, wherein the mass ratio of external swinging and circulation in the tail oil is 1:4, and the ratio of the external hydrocarbon oil to the circular tail oil is 1: 3. When the amount of the circulating tail oil is insufficient, hydrocarbon oil is used for replacing or supplementing the circulating tail oil, so that the mass ratio of the hydrocarbon oil and/or the tail oil, the catalyst and the biological tar is 1:0.005:1, the slurry bed reactor is a bubbling bed reactor, the operating temperature is 320 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 1000. The reaction index of the slurry bed reactor is shown in Table 3.

And (3) distilling and separating the reaction product of the slurry bed, wherein the fraction with the distillation range of more than 350 ℃ is tail oil, and the fraction with the distillation range of less than 350 ℃ is separated into water and light bio-oil. Wherein, the element analysis of the light bio-oil with the distillation range of less than 350 ℃ is shown in the table 4.

And step four, taking the light bio-oil obtained in the step three as a raw material, carrying out fixed bed hydrogenation reaction by using a second hydrogenation catalyst, and distilling and separating a product obtained in the hydrogenation reaction to obtain the chemical raw material and the liquid fuel, wherein the catalyst of the fixed bed reactor uses gamma-Al 2O3 as a carrier, and uses Ni, Mo and W as active components. Wherein the mass ratio of the active component to the carrier is 0.2:1, and the mass ratio of Ni, Mo and W calculated by oxides is 2:1: 1. The fixed bed reactor is a trickle bed reactor, the operating temperature is 400 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 500. The fixed reactor reaction index is shown in Table 5. Separating a small amount of water in the fixed bed hydrogenation product to obtain the refined biofuel oil. The elemental composition, distillation range and material accounting for biofuel oil are shown in tables 6, 7 and 8.

example 2

Step one, waste forest residues are used as biomass raw materials, the waste forest residues are pre-dried and crushed and then enter a rotary kiln pyrolysis reactor for pyrolysis reaction, the operating temperature of biomass pyrolysis is 300 ℃, the heating rate is 100 ℃/min, and pyrolysis products comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke are obtained; the distribution of the pyrolysis products obtained is shown in table 1. The elemental analysis of the bio-tar is shown in Table 2.

And step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier, grinding the pyrolysis semicoke to 40-200 meshes in advance, and preparing the slurry bed hydrogenation catalyst by taking iron oxyhydroxide as an active component. Wherein the ratio of the active components to the pyrolytic semicoke is 0.6:1 for later use;

and step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing the hydrocarbon oil for preparing the slurry in one part of the obtained tail oil, and swinging the other part of the obtained tail oil, wherein the mass ratio of external swinging and circulation in the tail oil is 1:10, and the ratio of the external hydrocarbon oil to the circular tail oil is 1: 3. When the amount of the circulating tail oil is insufficient, hydrocarbon oil is used for replacing or supplementing the circulating tail oil, so that the mass ratio of the hydrocarbon oil and/or the tail oil, the catalyst and the biological tar is 1:0.2:5, the slurry bed reactor is an airlift sleeve reactor, the operating temperature is 450 ℃, the operating pressure is 18MPa, the volume space velocity is 10.0h < -1 >, and the volume ratio of hydrogen to oil is 100. The reaction index of the slurry bed reactor is shown in Table 3.

and step four, taking the light bio-oil obtained in the step three as a raw material, carrying out fixed bed hydrogenation reaction by using a second hydrogenation catalyst, and distilling and separating a product obtained in the hydrogenation reaction to obtain the chemical raw material and the liquid fuel, wherein the catalyst of the fixed bed reactor uses gamma-Al 2O3 as a carrier, and uses Ni, Mo and W as active components. Wherein the mass ratio of the active component to the carrier is 0.2:1, and the mass ratio of Ni, Mo and W calculated by oxides is 2:1: 1. The fixed bed reactor is a trickle bed reactor, the operating temperature is 420 ℃, the operating pressure is 18MPa, the volume space velocity is 5.0h < -1 >, and the volume ratio of hydrogen to oil is 800. The fixed reactor reaction index is shown in Table 5. Separating a small amount of water in the fixed bed hydrogenation product to obtain the refined biofuel oil. The elemental composition, distillation range and material accounting for biofuel oil are shown in tables 6, 7 and 8.

example 3

Step one, using municipal refuse as a biomass raw material, classifying the municipal refuse, pre-drying and crushing the recyclable refuse, and then putting the classified municipal refuse into a fluidized bed pyrolysis reactor for pyrolysis reaction, wherein the operation temperature of biomass pyrolysis is 600 ℃, and the heating rate is 500 ℃/min, so as to obtain pyrolysis products comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke; the distribution of the pyrolysis products obtained is shown in table 1. The elemental analysis of the bio-tar is shown in Table 2.

And step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier, grinding the pyrolysis semicoke to 40-200 meshes in advance, and preparing the slurry bed hydrogenation catalyst by taking iron oxyhydroxide as an active component. Wherein the ratio of the active components to the pyrolytic semicoke is 0.6:1 for later use; and step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing the hydrocarbon oil for preparing the slurry in one part of the obtained tail oil, and swinging the other part of the obtained tail oil, wherein the mass ratio of external swinging and circulation in the tail oil is 1:10, and the ratio of the external hydrocarbon oil to the circular tail oil is 1: 3. When the amount of the circulating tail oil is insufficient, hydrocarbon oil is used for replacing or supplementing the circulating tail oil, so that the mass ratio of the hydrocarbon oil and/or the tail oil, the catalyst and the biological tar is 1:0.1:2, the slurry bed reactor is a forced slurry circulating reactor, the operating temperature is 200 ℃, the operating pressure is 10MPa, the volume space velocity is 5.0h < -1 >, and the hydrogen-oil volume ratio is 800. The reaction index of the slurry bed reactor is shown in Table 3.

And step four, taking the light bio-oil obtained in the step three as a raw material, carrying out fixed bed hydrogenation reaction by using a second hydrogenation catalyst, and distilling and separating a product obtained in the hydrogenation reaction to obtain the chemical raw material and the liquid fuel, wherein the catalyst of the fixed bed reactor uses gamma-Al 2O3 as a carrier, and uses Ni, Mo and W as active components. Wherein the mass ratio of the active component to the carrier is 0.2:1, and the mass ratio of Ni, Mo and W calculated by oxides is 2:1: 1. The fixed bed reactor is a trickle bed reactor, the operating temperature is 300 ℃, the operating pressure is 16MPa, the volume space velocity is 2.0h < -1 >, and the volume ratio of hydrogen to oil is 600. The fixed reactor reaction index is shown in Table 5. Separating a small amount of water in the fixed bed hydrogenation product to obtain the refined biofuel oil. The elemental composition, distillation range and material accounting for biofuel oil are shown in tables 6, 7 and 8.

Example 4

Firstly, shells such as coconut shells are used as biomass raw materials, the shells such as the coconut shells are pre-dried and crushed, and then enter a rotating cone pyrolysis reactor for pyrolysis reaction, the operation temperature of biomass pyrolysis is 500 ℃, the heating rate is 500 ℃/min, and pyrolysis products comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke are obtained; the distribution of the pyrolysis products obtained is shown in table 1. The elemental analysis of the bio-tar is shown in Table 2.

And step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier, grinding the pyrolysis semicoke to 40-200 meshes in advance, and preparing the slurry bed hydrogenation catalyst by taking iron oxyhydroxide as an active component. Wherein the ratio of the active components to the pyrolytic semicoke is 0.5:1 for later use; the pyrolysis semicoke is pre-activated, and the pre-activation step comprises the following steps:

Step one, putting the pyrolysis semicoke obtained in the step one into a NaOH solution with the mass fraction of 12 wt%, continuously raising the temperature of the NaOH solution to 100 ℃ while stirring, and reacting for 4 hours, wherein the mass ratio of the pyrolysis semicoke to the NaOH solution is 1: 8; then taking out the pyrolysis semicoke, and cleaning the pyrolysis semicoke by using distilled water until the surface pH value is neutral;

secondly, raising the temperature of the activation furnace to 600 ℃, preheating for 30min, and introducing carbon dioxide for 8min, wherein the flow rate of the carbon dioxide is 8 mL/min; and (3) placing the neutral pyrolysis semicoke obtained in the first step into an activation furnace, raising the temperature in the furnace to 900 ℃, adjusting the flow rate of carbon dioxide to 12mL/min, and activating for 4 h.

TABLE 1 pyrolysis product distribution

TABLE 2 elemental analysis of biological Tar

TABLE 3 reaction index of slurry bed reactor

TABLE 4 elemental analysis of slurry bed hydrogenated light bio-oil

TABLE 5 fixed bed reactor reaction index

TABLE 6 elemental analysis of fixed bed hydrogenated biofuels

TABLE 7 fixed bed hydrogenation biofuel distillation range

TABLE 8 materials accounting

As can be seen from table 8, the biomass has many sources, including municipal wastes, animals and plants, and forestry wastes, and is finally converted into dry gas, liquefied gas, gasoline components, pyrolysis semicoke, acid gas, low calorific value gas, and water by the process provided by the present invention, so that the process of converting biomass into chemical raw materials and liquid fuels is realized, and the process has the advantages of simple operation, strong continuous operability, and high conversion efficiency.

Comparative example 1

Firstly, using coconut shells as biomass raw materials, pre-drying and crushing the coconut shells, and then, introducing the coconut shells into a rotating cone pyrolysis reactor for pyrolysis reaction, wherein the operating temperature of biomass pyrolysis is 500 ℃, the heating rate is 500 ℃/min, and pyrolysis products comprising pyrolysis gas, biological tar, pyrolysis water and pyrolysis semicoke are obtained;

and step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier, grinding the pyrolysis semicoke to 40-200 meshes in advance, and preparing the slurry bed hydrogenation catalyst by taking iron oxyhydroxide as an active component. Wherein the ratio of the active components to the pyrolytic semicoke is 0.5:1 for later use; wherein the ratio of the active components to the pyrolytic semicoke is 0.5:1 for later use;

Step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, allowing the slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, and performing distillation separation on the hydrogenated biological oil to obtain light biological oil, water and tail oil, wherein the mass ratio of the hydrocarbon oil, the catalyst and the biological tar is 1:0.005:1, and the distillation range of the hydrocarbon oil is shown in table 9; the slurry bed reactor is a bubbling bed reactor, the operating temperature is 320 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 1000.

TABLE 9 hydrocarbon oil distillation range

And (3) distilling and separating the reaction product of the slurry bed, wherein the fraction with the distillation range of more than 350 ℃ is tail oil, and the fraction with the distillation range of less than 350 ℃ is separated into water and light bio-oil.

And step four, taking the light bio-oil obtained in the step three as a raw material, carrying out fixed bed hydrogenation reaction by using a second hydrogenation catalyst, and distilling and separating a product obtained in the hydrogenation reaction to obtain the chemical raw material and the liquid fuel, wherein the catalyst of the fixed bed reactor uses gamma-Al 2O3 as a carrier, and uses Ni, Mo and W as active components. Wherein the mass ratio of the active component to the carrier is 0.2:1, and the mass ratio of Ni, Mo and W calculated by oxides is 2:1: 1. The fixed bed reactor is a trickle bed reactor, the operating temperature is 340 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 500. The fixed reactor reaction indices are given in Table 6.

TABLE 10 elemental analysis of fixed bed hydrogenated biofuels

TABLE 11 fixed bed hydrogenation biofuel distillation range

TABLE 12 COMPARATIVE EXAMPLE 1 materials accounting

It can be seen from tables 8 and 12 that, when the feed straw and hydrogen are the same, the material balance of comparative example 1 is similar to that of example 1 when the tail oil replaces part of the hydrocarbon oil to prepare the slurry, the distillation range distribution of the fuel can be controlled through tail oil circulation, the hydrocarbon oil is less supplemented, and the biomass utilization rate is improved.

Comparative example 2

And step two, preparing a first hydrogenation catalyst by taking the pyrolysis semicoke obtained in the step one as a carrier, grinding the pyrolysis semicoke to 40-200 meshes in advance, and preparing the slurry bed hydrogenation catalyst by taking iron oxyhydroxide as an active component. Wherein the ratio of the active components to the pyrolytic semicoke is 0.5:1 for later use; the pyrolysis semicoke is pre-activated, and the pre-activation step is as follows:

Putting the pyrolysis semicoke obtained in the step one into a NaOH solution with the mass fraction of 12 wt%, continuously raising the temperature of the NaOH solution to 100 ℃ while stirring, and reacting for 4 hours, wherein the mass ratio of the pyrolysis semicoke to the NaOH solution is 1: 8; then taking out the pyrolysis semicoke, and cleaning the pyrolysis semicoke by using distilled water until the surface pH value is neutral;

And step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing the hydrocarbon oil for preparing the slurry in one part of the obtained tail oil, and swinging the other part of the obtained tail oil, wherein the mass ratio of external swinging and circulation in the tail oil is 1:4, and the ratio of the external hydrocarbon oil to the circular tail oil is 1: 3. When the amount of the circulating tail oil is insufficient, hydrocarbon oil is used for replacing or supplementing the circulating tail oil, so that the mass ratio of the hydrocarbon oil and/or the tail oil, the catalyst and the biological tar is 1:0.3:1, the slurry bed reactor is a bubbling bed reactor, the operating temperature is 320 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 1000.

And step four, taking the light bio-oil obtained in the step three as a raw material, carrying out fixed bed hydrogenation reaction by using a second hydrogenation catalyst, and distilling and separating a product obtained in the hydrogenation reaction to obtain the chemical raw material and the liquid fuel, wherein the catalyst of the fixed bed reactor uses gamma-Al 2O3 as a carrier, and uses Ni, Mo and W as active components. Wherein the mass ratio of the active component to the carrier is 0.2:1, and the mass ratio of Ni, Mo and W calculated by oxides is 2:1: 1. The fixed bed reactor is a trickle bed reactor, the operating temperature is 400 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 500.

Comparative example 3

Secondly, raising the temperature of the activation furnace to 600 ℃, preheating for 30min, and introducing carbon dioxide for 8min, wherein the flow rate of the carbon dioxide is 8 mL/min; and (3) placing the pyrolysis semicoke obtained in the step one into an activation furnace, raising the temperature in the furnace to 900 ℃, adjusting the flow rate of carbon dioxide to 12mL/min, and activating for 4 h.

And step three, preparing the biological tar obtained in the step one, the first hydrogenation catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the obtained slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing the hydrocarbon oil for preparing the slurry in one part of the obtained tail oil, and swinging the other part of the obtained tail oil, wherein the mass ratio of external swinging and circulation in the tail oil is 1:4, and the ratio of the external hydrocarbon oil to the circular tail oil is 1: 3. When the amount of the circulating tail oil is insufficient, hydrocarbon oil is used for replacing or supplementing the circulating tail oil, so that the mass ratio of the hydrocarbon oil and/or the tail oil, the catalyst and the biological tar is 1:0.2:1, the slurry bed reactor is a bubbling bed reactor, the operating temperature is 320 ℃, the operating pressure is 8MPa, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 1000.

The difference between the example 1 and the comparative examples 2-3 is that the activation mode of the pyrolysis semicoke obtained in the step one is different, the example 1 adopts the combination of alkali liquor activation and high-temperature activation, the comparative examples 2 and 3 respectively adopt alkali liquor activation and high-temperature activation, and in order to ensure that the slurry bed hydrogenation reaction reaches the reaction equilibrium in the same time, the amount of the catalyst used in the comparative examples 2 and 3 is 6 times and 4 times of that used in the example 1, which shows that the activity of the first hydrogenation catalyst obtained in the example 1 is obviously better than that of the comparative examples 2 and 3.

In the present invention, the volume values of the gas and the liquid used are both values of 25 ℃ and 1 atm, unless otherwise specified.

as described above, the present invention includes at least the following advantageous effects: firstly, the biomass conversion process provided by the invention can be operated continuously for a long period; secondly, in the method for preparing chemical raw materials and liquid fuel by using biomass, the biomass pulping process is simple, the operation is easy, and the method can be popularized to a biomass recycling project in a large range; thirdly, in the method for preparing chemical raw materials and liquid fuel by using biomass, the pyrolysis semicoke is used as a carrier for preparing the hydrogenation catalyst, the activation process is innovative, and the obtained catalyst has good catalytic activity.

While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention is intended, and further modifications may readily occur to those skilled in the art, whereby the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims

1. The method for preparing chemical raw materials and liquid fuel by biomass is characterized by comprising the following steps:

2. The method for preparing chemical raw materials and liquid fuels from biomass according to claim 1, wherein the biomass raw materials in the first step comprise plants, animals, agricultural and forestry wastes, municipal wastes and industrial wastes.

3. The method for preparing chemical raw materials and liquid fuels from biomass as claimed in claim 2, wherein the operating temperature of the fixed bed reactor in the fourth step is 200-420 ℃, the operating pressure is 2-18 MPa, the volume space velocity is 0.01-5.0 h < -1 >, and the volume ratio of hydrogen to oil is 200-; the active component of the second hydrogenation catalyst is one or more of VIB group and/or VIII group metals.

4. A method for preparing chemical raw materials and liquid fuels from biomass as claimed in claim 3, wherein the pyrolysis reaction in the first step is carried out in a rotary cone, a rotary kiln, a vertical furnace or a fluidized bed.

5. The method for preparing chemical raw materials and liquid fuels from biomass as recited in claim 3, wherein the temperature rise rate of the pyrolysis reaction in the first step is 10-10000 ℃/min.

6. The method for preparing chemical raw materials and liquid fuels from biomass as recited in claim 3, wherein the particle size of the pyrolysis semicoke carrier in the second step is 10-1000 um.

7. The method for preparing chemical raw materials and liquid fuels from biomass according to claim 3, wherein the hydrocarbon oil in step three comprises one or more of animal oil, vegetable oil, chemical oil products produced by the process, straight-run diesel oil, straight-run wax oil, catalytic cracking cycle oil, catalytic cracking diesel oil, catalytic cracking wax oil, coking diesel oil and coking wax oil.

8. The method for preparing chemical raw materials and liquid fuels by using the biomass as recited in claim 3, wherein the slurry bed hydrogenation reactor in the third step is a bubbling reactor, an airlift sleeve reactor or a forced slurry circulation reactor.

9. the method for preparing chemical raw materials and liquid fuels from biomass as recited in claim 3, wherein the other part of tail oil obtained by distillation and separation of hydrogenated bio-oil in the third step is thrown externally, wherein the volume ratio of the tail oil for circulation to the tail oil thrown externally is 0.1-10: 1.

10. The method for preparing chemical raw materials and liquid fuels from biomass according to claim 3, wherein the pyrolysis semicoke is pre-activated in the second step, and the pre-activation step comprises: