阅读说明：本技术 一种生产生物柴油的加氢工艺 (Hydrogenation process for producing biodiesel ) 是由 陈松 王康县 李广慈 李学兵 范芮堃 宋彦超 王�忠 于 2020-10-10 设计创作，主要内容包括：本发明公开了一种生产生物柴油的加氢工艺,该方法包括：(1)可再生生物质油脂原料与包含ⅤB、ⅥB和Ⅷ族元素组分的液态催化剂按0.01～1％比例混合后进入连续式加氢反应器,在2～20MPa的加氢条件200～400℃的反应温度下保持0.3～3小时反应；(2)反应物出来后进入高低压分离系统分离出液相和气相；(3)气相的循环氢返回作为循环氢,液相分离出水后进入残渣分离系统；(4)加氢尾渣自分离系统出装置,脱渣液相产物进入加氢提质提质或异构改质系统改质；(5)产物进入产品分离系统得到轻重产品即高十六烷值的生物柴油。该发明催化剂合成方式比较简单,原料易得,绿色环保,生成的生物柴油具有较高的十六烷值,性能优异。(The invention discloses a hydrogenation process for producing biodiesel, which comprises the following steps: (1) mixing a renewable biomass grease raw material and a liquid catalyst containing VB, VIB and VIII group element components according to a proportion of 0.01-1%, then feeding the mixture into a continuous hydrogenation reactor, and keeping the mixture for reaction for 0.3-3 hours under a hydrogenation condition of 2-20 MPa and at a reaction temperature of 200-400 ℃; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase; (3) the gas-phase recycle hydrogen is returned as recycle hydrogen, and the liquid-phase separated water enters a residue separation system; (4) the hydrogenation tailings are discharged from the system, and the deslagged liquid-phase product enters a hydrogenation upgrading system or an isomerization upgrading system for upgrading; (5) the product enters a product separation system to obtain a light and heavy product, namely the biodiesel with high cetane number. The catalyst has the advantages of simple synthesis mode, easily obtained raw materials, environmental protection, and high cetane number and excellent performance of the generated biodiesel.)

1. A hydrogenation process for producing biodiesel is characterized in that: the method comprises the following process steps: (1) mixing a biomass raw material and a liquid catalyst in proportion, then feeding the mixture into a continuous hydrogenation reactor, and keeping the mixture for a retention time to react under a set hydrogenation condition; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase; (3) the gas-phase recycle hydrogen is returned as recycle hydrogen, and the liquid-phase separated water enters a residue separation system; (4) the hydrogenation tailings are discharged from the separation system, and the deslagged liquid-phase product enters a hydrogenation upgrading system or an isomeric upgrading system for upgrading; (5) and the product enters a product separation system to obtain light and heavy products.

2. The hydrogenation process for producing biodiesel according to claim 1, wherein: the hydrogenation process is a process for converting a biomass feedstock into biodiesel having a high cetane number.

3. The hydrogenation process for producing biodiesel according to claim 1, wherein: the reaction residence time is 0.3-3 hours, the residence time can be measured according to the empty tower volume airspeed of the reactor, the empty tower volume airspeed is the ratio of unit time or hour feeding amount raw materials to the volume of the reactor, and the volume airspeed is 0.3-3.0.

4. The hydrogenation process for producing biodiesel according to claim 1, wherein: the liquid catalyst is a liquid artificially-synthesized catalyst containing VB, VIB and VIII element components, and the addition amount of the liquid catalyst is 0.01-1%.

5. The hydrogenation process for producing biodiesel according to claim 1, wherein: the hydrogenation condition is a reaction process in which hydrogen, a liquid catalyst and a raw material coexist at a reaction temperature of 200-400 ℃ and a pressure of 2-20 MPa.

6. The hydrogenation process for producing biodiesel according to claim 1, wherein: the continuous hydrogenation reactor comprises a suspension slurry bed, a suspension boiling bed or a full back-mixing suspension bed hydrogenation reactor.

7. The hydrogenation process for producing biodiesel according to claim 1, wherein: the biodiesel refers to a diesel component with high cetane number prepared by hydrogenation process, and the cetane index of the diesel component is not less than 70, preferably not less than 90.

8. The hydrogenation process for producing biodiesel according to claim 1, wherein: the biomass raw material comprises vegetable oil and/or animal fat and other renewable biomass grease.

Technical Field

The invention relates to a hydrogenation process for producing biodiesel, and relates to the field of new energy.

Background

The continuous decrease of petroleum resources and the increasingly strict environmental requirements are that the development of renewable green alternative energy sources is a necessary trend, and the biodiesel gradually enters the field of the public.

The first generation biodiesel refers to fatty acid methyl ester obtained by transesterification of triglyceride and methanol. Compared with common petroleum diesel, the first-generation biodiesel has the advantages of high cetane number, high flash point, low sulfur content, capability of utilizing waste grease as a raw material and the like. However, the first generation of biodiesel also has the problems of single raw material utilization variety, complex process, multiple equipment, excessive methanol used in the reaction process, corresponding methanol recovery device in the subsequent process, high energy consumption, serious influence on the yield and quality of biodiesel due to free fatty acid and water in the grease raw material, difficult recovery of esterification products, high cost, secondary environmental pollution caused by discharge of waste alkali liquor and waste acid liquor in the production process, and the like, and the main component of fatty acid methyl ester of the first generation of biodiesel also has certain problems in practical application due to the defect determined by the self-property: such as poor low-temperature fluidity, condensation, higher cold filter plugging point, lower heat value, higher viscosity, higher density, easy oxidation deterioration and the like.

In view of the above disadvantages, the oil treatment is carried out by a deep hydrogenation process. The grease is subjected to catalytic hydrogenation under the conditions of high temperature and high pressure to generate straight-chain alkane, which is the second generation biodiesel. The second generation biodiesel is internationally called green diesel and its component is C₁₂～C₂₀Alkane (mostly C)₁₅～C₁₈) Compared with the first-generation biodiesel, the second-generation biodiesel has the structure and the performance closer to those of petroleum diesel, has the characteristics of excellent blending property, low-temperature fluidity and the like, can be added into the petroleum diesel in a larger proportion, and has a wider application range.

CN201310441820 discloses a production method of biodiesel, which comprises the steps of raw oil pretreatment, esterification, ester exchange, dealcoholization, water washing, distillation and deodorization, methanol rectification recovery, glycerol purification recovery and the like. The method is a production method of first-generation biodiesel, and has the problems of high energy consumption of first-generation biodiesel, difficult recovery of esterification products, high cost, secondary environmental pollution caused by discharge of waste alkali liquor and waste acid liquor in the production process, and the like.

CN201410018298.9 discloses a method for producing second-generation biodiesel by hydrogenation of illegal cooking oil. The method uses the illegal cooking oil as a raw material, the transition metal phosphide as a catalyst, the hydrogen pressure is 0.5-10 MPa, and the reaction temperature is 200-480 ℃ for 4-6 h. The method has the advantage that the water is seriously polluted by the waste water generated by the phosphide.

CN201910648905.2 discloses a method for extracting and producing second-generation biodiesel from oil crops, which comprises the following steps: performing supercritical extraction on raw material crops, and pretreating extracts to obtain crude oil products; taking a crude oil product, and carrying out pre-esterification to obtain a pre-esterification product; taking the pre-esterification product, and performing transesterification to obtain fatty acid methyl ester; taking fatty acid methyl ester, and obtaining the second-generation biodiesel through hydrogenation reaction. The supercritical extraction conditions used by the method are harsh, and the equipment requirement is high; the catalytic hydrogenation uses a sulfuration type catalyst, sulfur is easy to lose in the reaction process, sulfur-containing compounds need to be continuously added to keep the activity of the catalyst, sulfur-containing waste gas and sulfur-containing waste liquid can be generated, a matched waste gas and wastewater treatment device needs to be added, and the investment and the operation cost are increased.

Disclosure of Invention

In view of the fact that the currently commonly produced biodiesel is the first-generation biodiesel with more defects and the hydrogenation process of the second-generation biodiesel is not mature enough, the invention aims to synthesize the second-generation biodiesel by hydrogenation by using a cheaper liquid catalyst.

In order to achieve the purpose, the technical scheme adopted by the invention is to hydrogenate the biomass raw material by using a liquid catalyst different from a traditional solid particle catalyst. The method comprises the following specific steps:

a hydrogenation process for producing biodiesel is characterized in that: the method comprises the following process steps: (1) mixing a biomass raw material and a liquid catalyst in proportion, then feeding the mixture into a continuous hydrogenation reactor, and keeping the mixture for a retention time to react under a set hydrogenation condition; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase; (3) the gas-phase recycle hydrogen is returned as recycle hydrogen, and the liquid-phase separated water enters a residue separation system; (4) the hydrogenation tailings are discharged from the separation system, and the deslagged liquid-phase product enters a hydrogenation upgrading system or an isomeric upgrading system for upgrading; (5) and the product enters a product separation system to obtain light and heavy products.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the hydrogenation process is a process for converting a biomass feedstock into biodiesel having a high cetane number.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the reaction residence time is 0.3-3 hours, the residence time can be measured according to the empty tower volume airspeed of the reactor, the empty tower volume airspeed is the ratio of unit time or hour feeding amount raw materials to the volume of the reactor, and the volume airspeed is 0.3-3.0.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the liquid catalyst is a liquid artificially-synthesized catalyst containing VB, VIB and VIII element components, and the addition amount of the liquid catalyst is 0.01-1%.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the hydrogenation condition is a reaction process in which hydrogen, a liquid catalyst and a raw material coexist at a reaction temperature of 200-400 ℃ and a pressure of 2-20 MPa.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the continuous hydrogenation reactor comprises a suspension slurry bed, a suspension boiling bed or a full back-mixing suspension bed hydrogenation reactor.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the biodiesel refers to a diesel component with high cetane number prepared by hydrogenation process, and the cetane index of the diesel component is not less than 70, preferably not less than 90.

The hydrogenation process for producing the biodiesel is characterized by comprising the following steps of: the biomass raw material comprises vegetable oil and/or animal fat and other renewable biomass grease.

The catalyst has the advantages of simple synthesis mode, easily obtained raw materials, environmental protection, and high cetane number and excellent performance of the generated biodiesel.

Detailed Description

The present invention will be further explained with reference to specific examples, but the present invention is not limited to the following embodiments.

Example 1

The liquid catalyst is ammonium molybdate by mass ratio: nickel nitrate: ammonium metatungstate: water is a 2:10:2:10 mixed solution.

The production process of the biodiesel comprises the following steps:

(1) uniformly stirring palm oil and a liquid catalyst with the mass fraction of 0.1% by using a stirrer, and then injecting the uniformly mixed raw materials into a suspension fluidized bed by using a pump for hydrogenation reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 9MPa, and the retention time is 2 hours; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase, the gas phase is recycled as circulating hydrogen, and the liquid phase separated water enters a residue separation system; (3) the deslag liquid is injected into an isomerization reforming reactor and is converted into biodiesel under the conditions that the reaction temperature is 360 ℃ and the reaction pressure is 8 MPa. The yield of the diesel oil component in the product is 78 percent, and the density is 0.7786g/cm³The sulfur content was 3.0mg/L, and the cetane number was 84.

Example 2

The liquid catalyst is nickel nitrate in mass ratio: ammonium metatungstate: water is a 10:2:10 mixed solution.

The production process of the biodiesel comprises the following steps:

(1) stirring soybean oil and a liquid catalyst with the mass fraction of 0.1 percent uniformly by using a stirrer, and then injecting the uniformly mixed raw materials into a suspension fluidized bed by using a pump for hydrogenation reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 9MPa, and the retention time is 2 hours; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase, the gas phase is recycled as circulating hydrogen, and the liquid phase separated water enters a residue separation system; (3) the deslag liquid is injected into an isomerization reforming reactor and is converted into biodiesel under the conditions that the reaction temperature is 360 ℃ and the reaction pressure is 8 MPa. The yield of the diesel component in the product is 80 percent, and the density is 0.7846g/cm³The sulfur content was 3.2mg/L, and the cetane number was 91.

Example 3

The liquid catalyst is ferric chloride in mass ratio: nickel nitrate: ammonium metatungstate: water is a mixed solution of 5:10:2: 10.

The production process of the biodiesel comprises the following steps:

(1) stirring soybean oil and a liquid catalyst with the mass fraction of 0.1 percent uniformly by using a stirrer, and then injecting the uniformly mixed raw materials into a suspension fluidized bed by using a pump for hydrogenation reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 9MPa, and the retention time is 2 hours; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase, the gas phase is recycled as circulating hydrogen, and the liquid phase separated water enters a residue separation system; (3) the deslag liquid is injected into an isomerization reforming reactor and is converted into biodiesel under the conditions that the reaction temperature is 360 ℃ and the reaction pressure is 8 MPa. The yield of the diesel oil component in the product is 78 percent, and the density is 0.7855g/cm³The sulfur content was 3.8mg/L, and the cetane number was 72.

Example 4

The liquid catalyst was 4% nickel naphthenate.

The production process of the biodiesel comprises the following steps:

(1) uniformly stirring palm oil and a liquid catalyst with the mass fraction of 0.1% by using a stirrer, and then injecting the uniformly mixed raw materials into a suspension fluidized bed by using a pump for hydrogenation reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 9MPa, and the retention time is 2 hours; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase, the gas phase is recycled as circulating hydrogen, and the liquid phase separated water enters a residue separation system; (3) the deslag liquid is injected into an isomerization reforming reactor and is converted into biodiesel under the conditions that the reaction temperature is 360 ℃ and the reaction pressure is 8 MPa. The yield of the diesel component in the product is 80 percent, and the density is 0.7726g/cm³The sulfur content was 3.3mg/L, and the cetane number was 79.

Example 5

The liquid catalyst was 7% cobalt isooctanoate.

The production process of the biodiesel comprises the following steps:

(1) uniformly stirring palm oil and a liquid catalyst with the mass fraction of 0.1% by using a stirrer, and then injecting the uniformly mixed raw materials into a suspension fluidized bed by using a pump for hydrogenation reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 9MPa, and the retention time is 2 hours; (2) the reactants enter a high-low pressure separation system after coming out to separate a liquid phase and a gas phase, and the gas phase is recycled as the circulating hydrogen and the liquidThe phase separation effluent enters a residue separation system; (3) the deslag liquid is injected into an isomerization reforming reactor and is converted into biodiesel under the conditions that the reaction temperature is 360 ℃ and the reaction pressure is 8 MPa. The yield of the diesel component in the product is 80 percent, and the density is 0.7748g/cm³The sulfur content was 3.2mg/L, and the cetane number was 83.

Example 6

The liquid catalyst is nickel nitrate in mass ratio: ammonium metatungstate: the synthesized nickel naphthenate waste liquid is a mixed solution with the ratio of 10:2: 10.

The production process of the biodiesel comprises the following steps:

(1) stirring soybean oil and a liquid catalyst with the mass fraction of 0.1 percent uniformly by using a stirrer, and then injecting the uniformly mixed raw materials into a suspension fluidized bed by using a pump for hydrogenation reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 9MPa, and the retention time is 2 hours; (2) after the reactants come out, the reactants enter a high-pressure and low-pressure separation system to separate a liquid phase and a gas phase, the gas phase is recycled as circulating hydrogen, and the liquid phase separated water enters a residue separation system; (3) the deslag liquid is injected into an isomerization reforming reactor and is converted into biodiesel under the conditions that the reaction temperature is 360 ℃ and the reaction pressure is 8 MPa. The yield of the diesel oil component in the product is 79 percent, and the density is 0.7846g/cm³The sulfur content was 4.4mg/L, and the cetane number was 95.