阅读说明：本技术 生物质制取化工原料和液体燃料的方法 (method for preparing chemical raw material and liquid fuel from biomass ) 是由 曾宿主 杨发新 王庆明 刘玉珍 刘艳艳 于 2019-08-05 设计创作，主要内容包括：本发明公开了一种生物质制取化工原料和液体燃料的方法,包括：步骤一、将生物质原料进行热解反应,得到包括热解气、生物焦油、热解水以及热解半焦的热解产物；步骤二、将所得的热解半焦作为载体制备第一加氢催化剂,备用；步骤三、将所得生物焦油、第一加氢催化剂、以及烃油制成浆料,所得浆料进入浆态床加氢反应器中进行加氢反应得到加氢生物油,将所得加氢生物油进行蒸馏分离得到轻质生物油、水以及尾油,所得尾油一部分循环替代烃油制备浆料,步骤四、将所得轻质生物油进行催化裂化得到所述化工原料和液体燃料。本发明所提供的生物质转化工艺制浆简单,可连续操作,所得产品可直接利用。(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, a 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, carrying out distillation separation on the obtained hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing the hydrocarbon oil with part of the obtained tail oil to prepare the slurry, and carrying out catalytic cracking on the obtained light biological oil 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, and the obtained product can be directly utilized.)

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

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 catalyst for later use by taking the pyrolysis semicoke obtained in the step one as a carrier;

Step three, preparing the biological tar obtained in the step one, the first catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing part of the tail oil with the hydrocarbon oil to prepare the slurry, and replacing or supplementing 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, performing catalytic cracking reaction by using a second catalyst, and distilling and separating the obtained product to obtain the chemical raw material and the liquid fuel, wherein the catalytic cracking reaction temperature is 400-700 ℃, the reaction pressure is 0.1-0.3 MPa, and the weight ratio of the second catalyst to the light bio-oil is 1-40: 1.

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 according to claim 2, wherein the catalytic cracking reaction in step four is carried out in a riser reactor.

4. The method for preparing chemical raw materials and liquid fuels from biomass as claimed in claim 2, wherein the second catalyst comprises zeolite, heat-resistant inorganic oxide and clay, and the weight ratio of zeolite, heat-resistant inorganic oxide and clay is 1-80: 1-99: 1-50.

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

6. The method for preparing chemical raw materials and liquid fuels from biomass according to claim 5, 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 5, 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 5, 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 5, 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 5, wherein the pyrolysis semicoke is pre-activated in the second step, and the pre-activation step comprises:

step one, cooling the pyrolysis semicoke obtained in the step one, then putting the cooled pyrolysis semicoke 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 h, 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.

Technical Field

The invention relates to the field of biomass application. More particularly, the invention relates to a method for preparing chemical raw materials and liquid fuels from biomass.

background

biomass, as the only material renewable resource, includes animals, plants, microorganisms and their excretions and metabolites. The biomass can be directly combusted to generate electricity, and can be further utilized as 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.

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.

it is still another object of the present invention to provide a method for preparing chemical raw materials and liquid fuels from biomass, which can convert biomass into directly usable chemical raw materials and high-value liquid fuels.

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 catalyst for later use by taking the pyrolysis semicoke obtained in the step one as a carrier;

step three, preparing the biological tar obtained in the step one, the first catalyst obtained in the step two and hydrocarbon oil into slurry, enabling the slurry to enter a slurry bed hydrogenation reactor for hydrogenation reaction to obtain hydrogenated biological oil, distilling and separating the hydrogenated biological oil to obtain light biological oil, water and tail oil, circularly replacing part of the tail oil with the hydrocarbon oil to prepare the slurry, and replacing or supplementing 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, performing catalytic cracking reaction by using a second catalyst, and distilling and separating the obtained product to obtain the chemical raw material and the liquid fuel, wherein the catalytic cracking reaction temperature is 400-700 ℃, the reaction pressure is 0.1-0.3 MPa, and the weight ratio of the second catalyst to the light bio-oil is 1-40: 1.

According to the technical scheme, the biomass is converted into the chemical raw materials and the high-value liquid fuel which can be directly utilized after pyrolysis, slurry bed hydrogenation and catalytic cracking, so that the continuous operability of the process for 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 catalytic cracking reaction in the fourth step is carried out in a riser reactor, the operating temperature of the riser reactor is 400-700 ℃, the reaction pressure is 0.1-0.3 MPa, and the volume space velocity is 1.0-50.0 h < -1 >; the weight ratio of the catalyst to the oil is 1-40: 1.

Preferably, the second catalyst comprises zeolite, refractory inorganic oxide and clay, wherein the zeolite is one or more of pentasil zeolite, beta zeolite and Y-type zeolite; the heat-resistant inorganic oxide is one or two of aluminum oxide and silicon oxide; the viscosity is one or more of kaolin, bentonite and clay, wherein the weight ratio of the zeolite, the heat-resistant inorganic oxide and the clay is 1-80: 1-99: 1-50.

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 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, cooling the pyrolysis semicoke obtained in the step one, then putting the cooled pyrolysis semicoke 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 h, 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, products obtained by the biomass conversion process provided by the invention are chemical raw materials which can be directly utilized and high-value liquid fuels; secondly, the biomass conversion process provided by the invention can be operated continuously for a long period; thirdly, the invention adopts a slurry bed reaction form to treat the biological tar, can be operated for a long period, has no pressure drop and has high conversion rate; in the method for preparing chemical raw materials and liquid fuels by using the biomass, the biomass pulping process is simple and easy to operate, and can be popularized to a biomass recycling project in a large range; and fifthly, 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 with reference to specific examples, so that those skilled in the art can implement the invention with reference to the description.

It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.