CN111778056A - Method for producing rubber filling oil by adopting direct coal liquefaction oil - Google Patents

Method for producing rubber filling oil by adopting direct coal liquefaction oil Download PDF

Info

Publication number
CN111778056A
CN111778056A CN202010582672.3A CN202010582672A CN111778056A CN 111778056 A CN111778056 A CN 111778056A CN 202010582672 A CN202010582672 A CN 202010582672A CN 111778056 A CN111778056 A CN 111778056A
Authority
CN
China
Prior art keywords
catalyst
oil
reaction
hydrofining
hydro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010582672.3A
Other languages
Chinese (zh)
Inventor
单贤根
舒歌平
章序文
杨葛灵
王洪学
高山松
曹雪萍
韩来喜
陈茂山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
Ordos Coal to Liquid Branch of China Shenhua Coal to Liquid Chemical Co Ltd
Original Assignee
China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
Ordos Coal to Liquid Branch of China Shenhua Coal to Liquid Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Shenhua Coal to Liquid Chemical Co Ltd, Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd, Ordos Coal to Liquid Branch of China Shenhua Coal to Liquid Chemical Co Ltd filed Critical China Shenhua Coal to Liquid Chemical Co Ltd
Priority to CN202010582672.3A priority Critical patent/CN111778056A/en
Publication of CN111778056A publication Critical patent/CN111778056A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/008—Controlling or regulating of liquefaction processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to the field of coal chemical industry, and discloses a method for producing rubber filling oil by adopting direct coal liquefaction oil, which comprises the following steps: (1) in the presence of hydrogen, contacting a fraction with a distillation range of more than M obtained by fractionating the direct coal liquefaction oil with a catalyst to carry out hydrofining reaction to obtain a hydrofining effluent, wherein M is an arbitrary value between 300-360 ℃, and the catalyst comprises a hydrofining catalyst; (2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent; (3) and in the presence of hydrogen, contacting the hydroupgrading effluent with a hydrofinishing catalyst to perform further hydrofinishing reaction, and separating the obtained product to obtain the rubber filling oil. The rubber filling oil produced by the method has the characteristics of good low-temperature performance and good processability.

Description

Method for producing rubber filling oil by adopting direct coal liquefaction oil
Technical Field
The invention relates to the field of coal chemical industry, in particular to a method for producing rubber filling oil by adopting direct coal liquefaction oil.
Background
Rubber is a high polymer having high elasticity, toughness and strength, and has a long molecular chain structure, and in order to provide good processability to rubber, it is necessary to make the molecules slide easily, and for this purpose, a method of adding rubber oil is generally used.
Rubber oils are generally classified into three major classes, paraffin-based, cycloalkyl and aromatic. The paraffin-based rubber oil has good oxidation resistance and light stability, but relatively poor emulsibility, compatibility and low-temperature property, so that the paraffin-based rubber oil has poor compatibility with rubber in many application occasions and cannot provide good processing performance; the compatibility of the aromatic rubber oil and rubber is best, the produced rubber product has high strength, large addition amount and low price, but has dark color, large pollution and large toxicity; the naphthenic base rubber oil has the characteristics of paraffin base and aromatic base, has better emulsibility and compatibility, no pollution and no toxicity, is suitable for more rubber types, has wide application and is the most ideal rubber oil.
However, the reserves of naphthenic base crude oil only account for 2.2% of the total reserves of crude oil, and the demands of people on healthy and environment-friendly products are increasing, and the demands of environment-friendly high-grade white rubber and plastic filling oil are increasing. Therefore, the method has great practical significance for widening the raw material of the rubber oil and improving the processing technology of the rubber oil.
CN102485839B at a density of 950-3Kinematic viscosity at 100 ℃ of 200-2The rubber oil base oil product obtained by the visbreaking-hydrogenation combined process by using the crude oil or naphthenic base atmospheric residue as the raw material meets the product enterprise standards of KN4006 and KN4010, has the characteristics of moderate viscosity, light color, low pour point, small ultraviolet absorbance and the like, expands the raw material sources of the rubber oil base oil, but the raw material sources are still limited to petroleum sources.
CN104593063A takes medium and low temperature coal tar as raw material, firstly, proper fraction (light fraction with cutting point of 480-. The rubber filling base oil has the characteristics of good low-temperature fluidity, good intersolubility with rubber and good oxidation stability, but the product recovery rate can only reach 41.74 wt.%, and still needs to be further improved.
The direct coal liquefaction technology is taken as an important guarantee of energy in China, the direct coal liquefaction oil product has the characteristics of low sulfur and nitrogen content and high aromatic hydrocarbon content, and how to efficiently carry out comprehensive utilization of the direct coal liquefaction oil is an important link for improving the economy of the direct coal liquefaction oil product according to the product characteristics. At present, no process report of producing rubber filling oil by using direct coal liquefaction oil exists, so the process needs to be developed urgently to widen the industrial application range of the direct coal liquefaction technology and provide the rubber filling oil with good low-temperature performance and good processability.
Disclosure of Invention
The invention aims to solve the problems of limited production approach, limited raw material resources, low product recovery rate and the like of the rubber filling oil in the prior art, and provides a method for producing the rubber filling oil by adopting direct coal liquefaction oil.
In order to achieve the above objects, the present invention provides, in one aspect, a method for producing rubber extender oil using coal direct liquefaction oil, the method comprising the steps of:
(1) in the presence of hydrogen, contacting a fraction with a distillation range of more than M obtained by fractionating the direct coal liquefaction oil with a catalyst to carry out hydrofining reaction to obtain a hydrofining effluent, wherein M is an arbitrary value between 300-360 ℃, and the catalyst comprises a hydrofining catalyst;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydroupgrading effluent with a hydrofinishing catalyst to perform further hydrofinishing reaction, and separating the obtained product to obtain the rubber filling oil.
Through the technical scheme, the invention has the following advantages:
(1) the method for producing the rubber filling oil by taking the direct coal liquefaction oil as the raw material for the first time opens up a new way for the quality improvement and utilization of the direct liquefaction oil, effectively prolongs the industrial chain for utilizing the direct liquefaction oil, and widens the raw material source of the rubber filling oil;
(2) the process flow is short, the energy consumption is low, the product quality is good, and the yield is high;
(3) the rubber filling oil with good low temperature and operation performance can be obtained;
(4) according to the invention, the raw rubber oil is processed and prepared by cutting the directly liquefied heavy fraction of coal, so that the utilization efficiency of a reactor of the catalyst can be effectively improved, the yield of a target product is improved, and the process investment is reduced;
(5) other fractions after hydrotreating in the method provided by the invention can be used as blending components of gasoline and diesel oil or raw materials of other special oil products, so that the utilization rate of the raw materials is improved.
Drawings
FIG. 1 is a schematic diagram of a process for producing rubber extender oil from coal-derived liquefied oil according to the present invention.
Description of the reference numerals
1 is coal direct liquefaction oil, 2 is a fractionating tower, 3 is a fraction below 160 ℃, 4 is a fraction at 160-.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for producing rubber filling oil by using direct coal liquefaction oil, which comprises the following steps:
(1) in the presence of hydrogen, contacting a fraction with a distillation range > M obtained by fractionating the coal direct liquefaction oil with a catalyst to carry out hydrofining reaction to obtain a hydrofining effluent, wherein M is an arbitrary value between 300 and 360 ℃ (preferably 320 ℃), and the catalyst comprises a hydrofining catalyst;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydroupgrading effluent with a hydrofinishing catalyst to perform further hydrofinishing reaction, and separating the obtained product to obtain the rubber filling oil.
According to the invention, the hydrofining reaction in the step (1) aims to remove sulfur and/or nitrogen elements in the coal direct liquefaction oil and promote aromatic saturation. Thus, any hydrogenation reaction conditions that achieve the above objectives may be suitable for use in the process of the present invention.
Preferably, the conditions of the hydrofinishing reaction in step (1) include: the reaction pressure is 3-21MPa, the reaction temperature is 330--1. Wherein the volume ratio of the hydrogen to the oil is the distillation range obtained by fractionating the direct liquefied oil of hydrogen and coal>Volume ratio of fractions of M.
More preferably, the conditions of the hydrofinishing reaction in step (1) include: the reaction pressure is 10-15MPa, the reaction temperature is 350--1. Wherein the volume ratio of the hydrogen to the oil is the distillation range obtained by fractionating the direct liquefied oil of hydrogen and coal>Volume ratio of fractions of M.
According to a preferred embodiment of the present invention, wherein the catalyst in step (1) comprises a hydrogenation protection catalyst and a hydrofinishing catalyst. The hydrogenation protection catalyst is used for removing metal heteroatoms and part of inorganic impurities in the direct coal liquefaction oil. The hydrofining catalyst has the functions of removing sulfur and/or nitrogen elements in the raw oil and promoting aromatic saturation. Therefore, any catalyst commonly used in the art that can perform the above-described functions can be suitably used in the process provided by the present invention.
According to a preferred embodiment of the present invention, wherein said fraction in step (1) is contacted with said hydrogenation protection catalyst and said hydrorefining catalyst in sequence. The contact mode comprises the following steps: hydrogen and raw materials react in a gas-liquid state in contact with the solid-phase catalyst.
Preferably, the volume ratio of the hydrogenation protection catalyst to the hydrofining catalyst is 1: 4-7, particularly preferably 1: 5.
according to a preferred embodiment of the present invention, the hydrogenation protection catalyst comprises a catalyst in which a porous refractory inorganic oxide is used as a carrier and a group VIB and/or group VIII metal is used as an active component.
Wherein the porous refractory inorganic oxide comprises at least one of alumina, silica and zirconia.
The group VIB and/or group VIII metal comprises at least one of W, Mo, Co, and Ni.
More preferably, the hydrofining catalyst further contains an auxiliary agent, and the auxiliary agent comprises at least one of P, Si, F and B.
According to a preferred embodiment of the present invention, wherein the porous refractory inorganic oxide may also be nano activated carbon.
In the hydrogenation protection catalyst, the content of the carrier can be 50-70 wt.%, the content of the active component can be 5-40 wt.%, and the content of the auxiliary agent can be 1-10 wt.%.
According to a preferred embodiment of the present invention, the hydrogenation protection catalyst may be a commercial catalyst having the above characteristics, or a catalyst having the above characteristics, which is prepared by itself according to the prior art.
According to a preferred embodiment of the present invention, wherein the hydrofinishing catalyst comprises a catalyst having Co, Ni, Mo and W as active metals. Any catalyst having such characteristics in the art may be suitable for use in the process provided by the present invention. For example, it may be a commercial catalyst or a catalyst having the above-mentioned characteristics, which is prepared by itself according to the prior art.
According to the present invention, it is preferred that the active component of the hydrofinishing catalyst catalyzes the hydrofinishing reaction in a sulfided state.
In the hydrofining catalyst, the content of the active component can be 10-40 wt.% in terms of oxide, and the content of the carrier can be 50-80 wt.%.
More preferably, the carrier of the hydrofinishing catalyst is alumina. The active component is a combination of a group VIB metal and a group VIII metal. The group VIB metal is Mo and/or W, and the content of the group VIB metal is 15-30 wt.% calculated by oxide. The group VIII metal is Co and/or Ni in an amount of 2-6 wt.% on an oxide basis. The specific surface area of the hydrorefining catalyst is not less than 100m2(iii) a pore volume of not less than 0.24 ml/g.
Further preferably, the specific surface area of the hydrorefining catalyst is 100-300m2Pore volume of 0.3-0.5 ml/g.
According to the invention, the purpose of the hydro-upgrading reaction in step (2) is to perform a selective ring opening on polycyclic cycloalkanes and/or aromatics and to preserve the side chain structure, thereby optimizing the physicochemical properties of the oil. Thus, any of the hydroupgrading reaction conditions commonly used in the art to achieve the above objectives may be applied to the process provided by the present invention.
Preferably, the conditions of the hydro-upgrading reaction include: the reaction pressure is 3-21MPa, the reaction temperature is 300-400 ℃, the volume ratio of hydrogen to oil is 400-2000:1, and the volume space velocity is 0.1-5h-1. Wherein the volume ratio of the hydrogen to the oil is the volume ratio of the hydrogen to the hydrofining effluent.
More preferably, the conditions of the hydro-upgrading reaction include: the reaction pressure is 10-15MPa, the reaction temperature is 320--1. Wherein the volume ratio of the hydrogen to the oil is the volume ratio of the hydrogen to the hydrofining effluent.
According to the present invention, preferably, the hydro-upgrading catalyst comprises a catalyst with amorphous silica-alumina and a modified molecular sieve as carriers and oxides of metals of group VIB and/or group VIII as active components.
In the hydro-upgrading catalyst, the content of the active component can be 14-60 wt.%, and the content of the carrier can be 30-80 wt.%.
Preferably, the weight ratio of the amorphous silica-alumina to the modified molecular sieve is 1-7: 1.
more preferably, the modified molecular sieve is a modified Y zeolite.
According to the invention, preferably, the amorphous silica-alumina has the characteristics of: silica 20-80 wt.%, alumina 20-50 wt.%. The specific surface area is 200-500m2Per gram, pore volume of 1.0-2.0mL/g, infrared acidity of 0.20-0.40 mmol/g.
More preferably, the amorphous silica-alumina is of the type: silica 30-75 wt.%, alumina 20-45 wt.%. The specific surface area is 300-450m2(ii) a pore volume of 1.3 to 1.7 mL/g.
According to the invention, preferably, the modified Y zeolite has the characteristics of: SiO 22And Al2O3In a molar ratio of 5 to 10: 1, unit cell constant of 2.410-2.445nm, relative crystallinity of 84-96%, infrared acidity of 0.2-0.7mmol/g, specific surface area of 300-800m2(iii) per gram, pore volume of 0.2-0.65 mL/g.
According to the present invention, preferably, the active component of the hydro-upgrading catalyst is a combination of a group VIB metal and a group VIII metal. The group VIB metal is Mo and/or W, and the content of the group VIB metal is 10-30 wt.% calculated by oxide. The group VIII metal is Co and/or Ni in an amount of 4-10 wt.% on an oxide basis.
According to the present invention, the specific surface area of the hydroupgrading catalyst is preferably not less than 200m2The pore volume is 0.2-0.7mL/g, the pore volume of pore diameter of 3-10nm accounts for 70-95% of the total pore volume, and the infrared acidity is 0.2-0.6 mmol/g.
More preferably, the specific surface area of the hydro-upgrading catalyst is 200-500m2The pore volume is 0.3-0.6mL/g, the pore volume of pore diameter of 3-10nm accounts for 85-95% of the total pore volume, and the infrared acidity is 0.3-0.5 mmol/g.
According to the present invention, wherein the catalyst in step (2) is a hydro-upgrading catalyst, any catalyst having the above characteristics may be used in the art. For example, the hydro-upgrading catalyst may be a commercial catalyst having the above characteristics, or a catalyst having the above characteristics, which is prepared by itself according to the prior art.
According to the present invention, wherein the purpose of said further hydrofinishing reaction (i.e. the hydrofinishing reaction) in step (3) is to further saturate the olefins and/or aromatics. Thus, any and all reaction conditions commonly used in the art for hydrofinishing to achieve the above objectives are applicable to the process provided herein.
Preferably, the conditions of the hydrofinishing reaction include: the reaction pressure is 3-15MPa, the reaction temperature is 140--1. Wherein the volume ratio of the hydrogen to the oil is the volume ratio of the hydrogen to the hydroupgrading effluent.
More preferably, the conditions of the hydrofinishing reaction include: the reaction pressure is 6-15 MPa; the reaction temperature is 160-220 ℃; the volume ratio of hydrogen to oil is 400-1000: 1; the volume space velocity is 0.6-1.5h-1. Wherein the volume ratio of the hydrogen to the oil is the volume ratio of the hydrogen to the hydroupgrading effluent.
According to the present invention, preferably, wherein the hydrofinishing catalyst in step (3) comprises a noble metal catalyst of a group VIII element and a group VIII noble metal element.
More preferably, the group VIII element in the hydrofinishing catalyst is Pd in an amount of 0.1 to 0.8 wt.% as the metal element and the group VIII metal is Pt in an amount of 0.1 to 0.5 wt.% as the metal element. The specific surface area of the hydrogenation and supplement refining catalyst is not less than 200m2(ii)/g, pore volume not less than 0.5mL/g, pore diameter not less than 8nm, active metal H2The adsorption amount is not less than 80 mL/g.
Further preferably, the specific surface area of the catalyst is 150-400m2Per g, pore volume of 0.3-0.6mL/g, pore diameter of 5-15nm, active metal H2The adsorption capacity is 90-150 mL/g.
According to a preferred embodiment of the present invention, wherein said hydrofinishing catalyst in step (3) may be any catalyst known in the art having the above characteristics. For example, the catalyst may be a commercial catalyst having the above-mentioned characteristics, or a noble metal catalyst having the above-mentioned characteristics, which is prepared by itself according to the prior art.
According to the invention, other fractions obtained after fractionation in the step (1) can be used for gasoline, diesel oil or other special oil raw materials.
Preferably, the fraction at <160 ℃ obtained after the fractionation in step (1) can be used as a gasoline blending component, the fraction at 160-290 ℃ can be used as a blending component for diesel, and the fraction at 290-330 ℃ can be used as a transformer oil base oil.
In the invention, the coal direct liquefaction oil refers to a coal direct liquefaction primary product, and the characteristics of the coal direct liquefaction primary product comprise: paraffin content of 0.5-3 wt.%, total naphthenes of 8-15 wt.%, total mono-cyclic aromatics of 40-45 wt.%, total bicyclic aromatics of 35-40 wt.%; tricyclic aromatics 5-10 wt.%. Density of 0.8-1.2g/cm3Viscosity of 4-5mm2At 100 deg.C, the condensation point is (-10) - (-5) deg.C.
According to the preferred embodiment of the present invention, specifically, a specific process flow provided by the present invention is shown in fig. 1, wherein the coal direct liquefaction oil 1 enters the fractionating tower 2 to obtain a fraction 3 below 160 ℃, a fraction 4 below 290 ℃, a fraction 6 above 330 ℃ and a fraction 5 above 330 ℃ respectively. Wherein the fraction 3 at the temperature of less than 160 ℃ can be used as a gasoline blending component, the fraction 4 at the temperature of 160-. And the fraction 5 with the temperature of more than 330 ℃ enters a hydrofining reaction zone 7, is contacted with a hydrofining catalyst in the presence of hydrogen 8, and is subjected to desulfurization, denitrification and deep saturation reaction of aromatic hydrocarbon in the presence of hydrogen and the hydrofining catalyst, so that the content of the aromatic hydrocarbon is reduced, and the oxidation stability index of the product is ensured. The hydrorefining reaction product 9 enters a hydroupgrading reaction zone 10, and the saturated ring opening is carried out on the two-ring and a small amount of tricyclic aromatic hydrocarbon, and meanwhile, the completeness of the side chain after the ring opening is kept, so that the ring-opened polycyclic aromatic hydrocarbon is changed into monocyclic or bicyclic aromatic hydrocarbon with multiple side chains. Then, after the hydro-upgrading product 11 is separated into gas 13 by a separator 12, the liquid phase product 14 enters a hydro-supplementation refining reactor 16 and is mixed with hydrogen 15 to further saturate aromatic hydrocarbon, so that the content of aromatic hydrocarbon above three rings is reduced, the supplementation refining product 17 enters a fractionating tower 16 to separate a small amount of by-product 19, and the liquid phase product 20 enters a pressure reducing tower to separate a small amount of by-product 22, so that a rubber filling oil product 23 is obtained.
The present invention will be further illustrated by the following specific examples, which should be noted to illustrate and describe the invention only and not to limit the invention.
In the following examples and comparative examples, the shenhua coal direct liquefaction oil is used as a raw material, and specific properties of the coal direct liquefaction oil are shown in table 1. The hydrogenation protective agent is an RGC-1 hydrogenation protective agent developed and produced by petrochemical research institute, the hydrofining catalyst is an RNC-2 hydrofining catalyst (vulcanized before use) developed and produced by petrochemical research institute, the hydrogenation modification catalyst is an RCC-1 commercial hydrotreating catalyst developed and produced by petrochemical research institute, and the hydrogenation complementary refining catalyst is an RLF-2 hydrotreating catalyst developed and produced by petrochemical research institute. The product quality testing methods of the following examples and comparative examples are shown in Table 3.
TABLE 1 direct coal liquefaction oil Properties
Figure BDA0002552978570000101
Example 1
(1) In the presence of hydrogen, fraction with the distillation range of more than 320 ℃ obtained by fractionating the Shenhua coal direct liquefied oil is sequentially contacted with a hydrogenation protection catalyst RGC-1 and a hydrofining catalyst RNC-2, the loading volume ratio of the RGC-1 to the RNC-2 is 1:5, and a hydrofining reaction is carried out to obtain a hydrofining effluent;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst RCC-1 to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydrogenation modified effluent with a hydrogenation complementary refining catalyst RLF-2 to perform further hydrogenation refining reaction, and distilling the obtained product under reduced pressure to obtain the rubber filling oil with the distillation range of more than 330 ℃.
The process conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Example 2
(1) In the presence of hydrogen, fraction with the distillation range of more than 320 ℃ obtained by fractionating Shenhua coal direct liquefied oil is contacted with a hydrogenation protection catalyst RGC-1 and a hydrofining catalyst RNC-2, and the filling volume ratio of the RGC-1 to the RNC-2 is 1: 4, carrying out hydrofining reaction to obtain a hydrofining effluent;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst RCC-1 to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydrogenation modified effluent with a hydrogenation complementary refining catalyst RLF-2 to perform further hydrogenation refining reaction, and distilling the obtained product under reduced pressure to obtain the rubber filling oil with the distillation range of more than 330 ℃.
The process conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Example 3
(1) In the presence of hydrogen, fraction with the distillation range of more than 360 ℃ obtained by fractionating Shenhua coal direct liquefied oil is contacted with a hydrogenation protection catalyst RGC-1 and a hydrofining catalyst RNC-2, and the filling volume ratio of the RGC-1 to the RNC-2 is 1: 7, carrying out hydrofining reaction to obtain a hydrofining effluent;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst RCC-1 to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydrogenation modified effluent with a hydrogenation complementary refining catalyst RLF-2 to perform further hydrogenation refining reaction, and distilling the obtained product under reduced pressure to obtain the rubber filling oil with the distillation range of more than 330 ℃.
The process conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Example 4
(1) In the presence of hydrogen, fraction with the distillation range of more than 300 ℃ obtained by fractionating Shenhua coal direct liquefied oil is contacted with a hydrogenation protection catalyst RGC-1 and a hydrofining catalyst RNC-2, and the filling volume ratio of the RGC-1 to the RNC-2 is 1:5, carrying out hydrofining reaction to obtain a hydrofining effluent;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst RCC-1 to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydrogenation modified effluent with a hydrogenation complementary refining catalyst RLF-2 to perform further hydrogenation refining reaction, and distilling the obtained product under reduced pressure to obtain the rubber filling oil with the distillation range of more than 330 ℃.
The process conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Example 5
The same raw materials as in example 1 were used to produce rubber extender oil, except that the hydrorefining reaction conditions, the hydroupgrading reaction conditions, and the hydrorefining reaction conditions were different from those in example 1, the specific hydrogenation process conditions are shown in table 2, and the product yield and properties are shown in table 3.
Comparative example 1
The same raw materials as in example 1 were used to produce rubber extender oil, except that the hydrorefined product was not subjected to hydro-upgrading, and the product yields and properties are shown in Table 3.
Comparative example 2
The same raw materials as in example 1 were used to produce rubber extender oil, except that the hydroupgraded product was not subjected to hydrorefining, and the product yields and properties are shown in Table 3.
Comparative example 3
The same embodiment as in example 1 was employed except that the fraction subjected to the hydrotreating reaction in step (1) was a fraction at 280 ℃ or lower. Specific product yields and properties are shown in table 3.
Comparative example 4
The same embodiment as in example 1 was employed except that the fraction subjected to the hydrotreating reaction in step (1) was a fraction having a temperature of 400 ℃ or higher. Specific product yields and properties are shown in table 3.
TABLE 2 Process conditions
Figure BDA0002552978570000131
TABLE 3 yield and Properties of the examples and comparative examples
Figure BDA0002552978570000141
From example 1, it can be seen that the physical properties of the rubber filling oil obtained by subjecting the coal direct liquefaction oil to the processing technologies of hydrofining, hydro-upgrading and hydro-refining meet the standards, and the indexes are better, which indicates that the process for processing the rubber filling oil by using the coal direct liquefaction oil provided by the invention is feasible.
As can be seen from the product properties of example 1 and comparative example 1, the rubber extender oil product obtained by only hydrofining the coal direct liquefaction oil without the hydro-upgrading process has a slightly higher target product oil yield, but has a higher pour point, a lower flash point, a fused ring aromatic PCA content of 3.4% (more than 3%), a content of 8 polycyclic aromatic hydrocarbons of 15mg/kg (more than 10mg/kg), and is not qualified.
It can be seen from the product properties of example 1 and comparative example 2 that the rubber filling oil after the coal direct liquefaction oil is subjected to three-stage hydrogenation of hydrofining, hydrogenation modification and hydrogenation complementary refining is obviously reduced in content of polycyclic aromatic hydrocarbons and pour point compared with that of comparative example 2, and the content of 8 polycyclic aromatic hydrocarbons (including benzopyrene) can meet the standard requirement.
It can be seen from the properties of the products of example 1, comparative example 3 and comparative example 4 that when the coal direct liquefaction oil fraction in the preferred temperature range of the invention is used for preparing the rubber filling oil, the product yield is high, the pour point is low, the low-temperature performance is good, the color is white and bright, and other product properties meet the standard requirements, particularly the polycyclic aromatic hydrocarbon PCA and PAHs can meet the environmental protection requirements.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method for producing rubber extender oil from coal direct liquefaction oil, comprising the steps of:
(1) in the presence of hydrogen, contacting a fraction with a distillation range of more than M obtained by fractionating the direct coal liquefaction oil with a catalyst to carry out hydrofining reaction to obtain a hydrofining effluent, wherein M is an arbitrary value between 300-360 ℃, and the catalyst comprises a hydrofining catalyst;
(2) in the presence of hydrogen, contacting the hydrofining effluent with a hydro-upgrading catalyst to carry out hydro-upgrading reaction to obtain a hydro-upgrading effluent;
(3) and in the presence of hydrogen, contacting the hydroupgrading effluent with a hydrofinishing catalyst to perform further hydrofinishing reaction, and separating the obtained product to obtain the rubber filling oil.
2. The process of claim 1, wherein the conditions of the hydrofinishing reaction in step (1) comprise: the reaction pressure is 3-21MPa, the reaction temperature is 330--1；
Preferably, the conditions of the hydrofinishing reaction include: the reaction pressure is 10-15MPa, the reaction temperature is 350--1。
3. The process of claim 1, wherein the catalyst in step (1) comprises a hydrogenation protection catalyst and a hydrogenation refining catalyst, and the fraction is sequentially contacted with the hydrogenation protection catalyst and the hydrogenation refining catalyst, and the volume ratio of the hydrogenation protection catalyst to the hydrogenation refining catalyst is 1: 4-7.
4. The process according to claim 1 or 3, wherein the hydrogenation protection catalyst in step (1) is a catalyst with porous refractory inorganic oxide as a carrier and metals of group VIB and/or group VIII as active components;
wherein the porous refractory inorganic oxide comprises at least one of alumina, silica and zirconia.
The group VIB and/or group VIII metal comprises at least one of W, Mo, Co, and Ni.
More preferably, the hydrofining catalyst further contains an auxiliary agent, and the auxiliary agent comprises at least one of P, Si, F and B.
5. The process of claim 1 or 3, wherein the hydrofinishing catalyst in step (1) is a catalyst with alumina as a carrier and metals of group VIB and/or group VIII as active components;
wherein the group VIB and/or group VIII metal comprises at least one of W, Mo, Co, and Ni;
preferably, the active component in the hydrofining catalyst catalyzes the hydrofining reaction in a sulfurized state;
more preferably, the active component of the hydrorefining catalyst is a combination of group VIB metals and group VIII metals, the group VIB metals being Mo and/or W in an amount of 15-30 wt.% calculated as oxides; the group VIII metal is Co and/or Ni, and the content of the group VIII metal is 2-6 wt.% calculated by oxide; the specific surface area of the hydrorefining catalyst is not less than 100m2(ii)/g; the pore volume is not less than 0.24 ml/g.
6. The process of claim 1, wherein the conditions of the hydro-upgrading reaction in step (2) comprise: the reaction pressure is 3-21MPa, the reaction temperature is 300-400 ℃, the volume ratio of hydrogen to oil is 400-2000:1, and the volume space velocity is 0.1-5h-1；
Preferably, the conditions of the hydro-upgrading reaction include: the reaction pressure is 10-15MPa, the reaction temperature is 320--1。
7. The method according to claim 1, wherein the hydro-upgrading catalyst in the step (2) is a catalyst which takes amorphous silica-alumina and modified molecular sieve as carriers and oxides of metals in the VIB group and/or VIII group as active components;
wherein the group VIB and/or group VIII metal comprises at least one of W, Mo, Co, and Ni;
the weight ratio of the amorphous silica-alumina to the modified molecular sieve is 1-7: 1;
preferably, the active component of the hydro-upgrading catalyst is a combination of a group VIB metal and a group VIII metal, wherein the group VIB metal is Mo and/or W, and the content of the group VIB metal is 10-30 wt.% calculated by oxides; the group VIII metal is Co and/or Ni, and the content of the group VIII metal is 4-10 wt.% calculated by oxide; the specific surface area of the catalyst is not less than 200m2(ii)/g; the pore volume is 0.2-0.7mL/g, the pore volume with the pore diameter of 3-10nm accounts for 70-95% of the total pore volume, and the infrared acidity is 0.2-0.6 mmol/g;
more preferably, the pore volume of pores having a diameter of 3 to 10nm is 85 to 95% of the total pore volume.
8. The process of claim 1, wherein the conditions of the further hydrofinishing reaction in step (3) comprise: the reaction pressure is 3-15MPa, the reaction temperature is 140--1；
Preferably, the conditions of the further hydrofinishing reaction include: the reaction pressure is 6-15MPa, the reaction temperature is 160-220 ℃, the volume ratio of hydrogen to oil is 400-1: 1, and the volume space velocity is 0.6-1.5h-1。
9. The process of claim 1, wherein the hydrofinishing catalyst in step (3) is a noble metal catalyst comprising a group VIII element and a group VIII noble metal element;
preferably, wherein the group VIII element is Pd in an amount of 0.1 to 0.8 wt.% as the metal element, the group VIII metal is Pt in an amount of 0.1 to 0.5 wt.% as the metal element, and the specific surface area of the catalyst is not less than 200m2(ii)/g, pore volume not less than 0.5mL/g, pore diameter not less than 8nm, active metal H2The adsorption amount is not less than 80 mL/g.
10. The method according to claim 1, wherein the other fractions obtained after the fractionation in step (1) are used for gasoline, diesel oil or other special oil raw materials;
preferably, the fraction at <160 ℃ is used as a gasoline blending component, the fraction at 160-290 ℃ is used as a blending component of diesel oil, and the fraction at 290-340 ℃ is used as a transformer oil base oil.
CN202010582672.3A 2020-06-23 2020-06-23 Method for producing rubber filling oil by adopting direct coal liquefaction oil Pending CN111778056A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010582672.3A CN111778056A (en) 2020-06-23 2020-06-23 Method for producing rubber filling oil by adopting direct coal liquefaction oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010582672.3A CN111778056A (en) 2020-06-23 2020-06-23 Method for producing rubber filling oil by adopting direct coal liquefaction oil

Publications (1)

Publication Number Publication Date
CN111778056A true CN111778056A (en) 2020-10-16

Family

ID=72757654

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010582672.3A Pending CN111778056A (en) 2020-06-23 2020-06-23 Method for producing rubber filling oil by adopting direct coal liquefaction oil

Country Status (1)

Country Link
CN (1) CN111778056A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104593063A (en) * 2013-11-04 2015-05-06 中国石油化工股份有限公司 Production method of base oil of rubber filling oil from medium and low temperature coal tars
CN108977224A (en) * 2018-08-01 2018-12-11 国家能源投资集团有限责任公司 Transformer oil base oil and preparation method thereof
CN109321273A (en) * 2018-09-27 2019-02-12 国家能源投资集团有限责任公司 The method and apparatus for producing naphthenic base refrigerator oil base oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104593063A (en) * 2013-11-04 2015-05-06 中国石油化工股份有限公司 Production method of base oil of rubber filling oil from medium and low temperature coal tars
CN108977224A (en) * 2018-08-01 2018-12-11 国家能源投资集团有限责任公司 Transformer oil base oil and preparation method thereof
CN109321273A (en) * 2018-09-27 2019-02-12 国家能源投资集团有限责任公司 The method and apparatus for producing naphthenic base refrigerator oil base oil

Similar Documents

Publication Publication Date Title
CN102264871B (en) Integrated hydrocracking and dewaxing of hydrocarbons
JP4084664B2 (en) Method for producing middle distillate
WO2010009089A2 (en) Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil
RU2007141712A (en) METHOD FOR PRODUCING SEMI-PRODUCT WITH REDUCED NITROGEN CONTENT AND CATALYST FOR ITS IMPLEMENTATION
CN107254330B (en) Regeneration process for producing low-freezing-point lubricating oil base oil by using waste lubricating oil through total hydrogen method
CN101240191B (en) Method for producing lightweight fuel oil by coal tar heavy fractioning hydrogenation
CN110540871B (en) Processing method of naphthenic oil
CN110540872B (en) Naphthenic oil treatment process
CN1205312C (en) Process for coking full fraction oil hydrogenation refining
CN100345945C (en) Two-stage hydrocracking method for increasing yield of middle distillate oil
CN110938467A (en) Hydrocracking method
CN110616083B (en) Process for producing crude white oil
WO2009080679A1 (en) Process to prepare a gas oil and a base oil
CN109321273B (en) Method and device for producing naphthenic base refrigerator oil base oil
CN111778056A (en) Method for producing rubber filling oil by adopting direct coal liquefaction oil
CN101240192A (en) Method for producing high grade diesel oil by coal tar heavy fractioning hydrogenation
CN110540873B (en) Method for processing naphthenic oil
CN113122325B (en) Method for producing rubber filling oil by catalytic cracking slurry oil
CN110540874B (en) Processing technology of naphthenic oil
CN1478866A (en) Method of gasoline desulfurization
CN1233797C (en) Hydrogenating modifying process for direct liquefying diesel oil of coal
CN109852417B (en) Production method of naphthenic base special oil product
CN111378494B (en) Processing method of Fischer-Tropsch synthetic oil
CN107557065B (en) Method for producing clean diesel oil by coal tar hydrogenation and system for method
CN116554925B (en) Waste plastic pyrolysis oil hydrogenation purification method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20201016

RJ01 Rejection of invention patent application after publication