CN105038853B - A kind of method utilizing FCC slurry and coal to refine oil altogether - Google Patents

Abstract

The invention discloses a method for co-refining oil with FCC oil slurry and coal. The technical problem to be solved is to provide an oil-coal co-refining method using FCC oil slurry and coal as raw materials, high coal concentration and high conversion rate. The technical scheme adopted is: first pulverize and dry the raw coal, mix the dried pulverized coal with oil slurry, catalyst, co-catalyst, and additives to form oil-coal slurry, enter the suspension bed reactor for hydrocracking reaction, separate The heavy components and light components are obtained. The heavy components are extracted by vacuum distillation and the separated light components are mixed into the hydrofinishing reactor for hydrofinishing. The hydrofinishing products are cut out of naphtha through multi-stage distillation. and diesel components. This technology solves the problems of the coal and oil refining industries while crossing fields, and builds a platform for the organic combination of efficient utilization of clean coal and deep processing of low-quality FCC oil slurry.

Description

A method of co-refining oil by utilizing FCC oil slurry and coal

technical field

The invention belongs to the technical field of coal direct liquefaction, and relates to a kerosene co-refining technology, in particular to a method for co-refining oil by utilizing FCC oil slurry and coal.

Background technique

With the improvement of industrial production and daily life, my country's demand for oil is also increasing rapidly. For a long period of time in the future, the main energy consumption in my country will still be coal. Due to energy structure problems, serious smog, water pollution Environmental problems such as pollution, so strengthening the comprehensive utilization of coal resources is still the main problem we have to face. The development of new coal chemical industry is of great significance to alleviate the dependence on foreign oil, reduce environmental hazards, and improve the comprehensive utilization rate of energy. Shaanxi Yanchang Petroleum (Group) has abundant and high-quality coal resources, and can produce high-quality light fuel oil through comprehensive utilization of these coal resources, thereby realizing the adjustment of China's energy structure. The co-refining method of FCC oil slurry and coal has no mature experience in China, and the technology for co-refining coal and oil slurry produced in northern Shaanxi is still blank in the world and domestically. In order to give full play to the resources and geographical advantages of Yanchang Oil Develop a co-refining method suitable for coal types and oil slurry in northern Shaanxi. Vigorously developing this sunshine industry will surely become an important foothold of my country's energy strategy and security.

China Coal Liquefaction Process (China Direct Coal Liquefaction Process, referred to as CDCL process) developed by the General Institute of Coal Science Research, patent number: CN1243813C. The process adopts the method of adding a separator in the middle of the two reactors to solve the secondary decomposition problem of the generated oil, and can simultaneously meet the short residence time of the light liquefied products of the coal liquefaction reaction in the reactor, difficult to liquefy and heavy coal liquefied products Longer residence time in the reactor and higher mass transfer rate and longer reaction time with gas phase hydrogen are required. However, the equipment investment has greatly increased, which is equivalent to adding a set of separation systems, including a set of separators, wear-resistant high-pressure differential pressure reducing valves, circulating gas compressors, and so on.

Coal Research Institute Publication No. 103074097A discloses a method and system for direct coal liquefaction. This technology has a first liquefaction reactor and a second liquefaction reactor for liquefaction reaction, and the liquefaction reaction product is obtained at the outlet of the second reactor, wherein Part of the liquefied product is returned to the inlet of the first liquefaction reactor for recycling. However, the reaction pressure of this technology is 30 PMa, the industrial production is difficult, and the oil yield is less than 60%.

Patent No. CN103773483A discloses a fluidized bed hydrogenation process to increase the yield of coal liquefied oil and light oil. This process is to first cut the FCC oil slurry into light fraction and heavy fraction, and then hydrogenate the heavy fraction and then combine with coal liquefied oil. Mixed into fluidized bed hydrotreating, the feature of this process is to increase the light oil yield of the unit, but the energy consumption of the unit is increased, and the requirements for raw materials are strict.

Compared with the prior art, the method for co-refining oil of FCC oil slurry and coal provided by the invention has the following advantages:

1) The coal concentration in the raw material can reach 35-55%, the reaction temperature range is 445-470°C, the coal conversion rate is >90%, and the liquid yield is >70%, all of which are higher than the existing coal direct liquefaction technology, reaching the level of heavy oil The purpose of improving the utilization of coal and efficient conversion of coal.

2) Compared with the existing direct coal liquefaction technology, this kerosene co-refining technology achieves a high liquid recovery and coal conversion rate with only one reactor, reducing production costs.

3) Using the wiped film evaporator for vacuum distillation technology to realize the separation of oil products and residues, reduce the boiling point of materials, thereby reducing energy consumption and avoiding thermal decomposition of products at high temperatures.

4) Use cheap iron-based catalysts, only add activated carbon additives, and the addition of catalysts and additives is very small, reducing cost investment.

5) The reactor has no internal components, and the gas-liquid-solid three-phase passes through the reactor in a plug-flow manner, and the process is simple.

6) This technology uses a wide range of raw materials, and has low requirements on the properties of raw materials. It can be used for co-refining of kerosene, and can also be used for separate processing of coal and heavy and low-quality oil (atmospheric and vacuum residue, catalytic oil slurry, coal tar, etc.).

7) Due to the full use of the good synergistic effect of coal and FCC oil slurry, the product yield is high, the energy consumption is low, and the product quality is good (it can directly produce diesel blended products with sulfur content meeting Euro IV and Euro V emission standards), liquid High yield and great production flexibility. It has significant economic and environmental benefits.

8) Compared with the direct liquefaction of coal, FCC oil slurry and coal refining oil have less investment per ton of oil, less hydrogen consumption, and higher oil yield.

9) Not affected by heavy metal content, colloid and asphaltene content, nitrogen content and sulfur content in raw materials.

Contents of the invention

The purpose of the present invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of method that utilizes FCC oil slurry and coal to refine oil together, this method can solve the solvent oil shortage problem of coal direct liquefaction technology and reduce operating severity, fully Utilize the good synergistic effect of FCC slurry and coal to increase liquid yield and coal conversion.

The purpose of the present invention is achieved through the following technical solutions:

The present invention utilizes the method for co-refining oil of FCC oil slurry and coal, comprises the following steps:

1) Preparation of oil-coal slurry

Heat and dry the pulverized coal until the particle size is less than 100 μm until the moisture content is less than 0.1%, and mix the qualified coal powder with catalyst, additive, co-catalyst, and FCC oil slurry heated to 100-150°C through a mechanical mixer , prepared into an oil-coal slurry with a solid content of 35-55wt%;

2) Suspension bed hydrocracking

The oil-coal slurry prepared in step 1) is pressurized to 20-23MPa by the feed high-pressure pump, mixed with circulating gas and hydrogen with a purity of 95-99%, and heated to 260-300°C in the heater, and then removed from the suspension The bottom of the bed reactor enters into the hydrocracking reaction;

3) Gas-liquid separation of hydrocracking products

The reaction product of step 2) enters the separation unit for gas-solid phase separation; the solid phase obtained from the separation is residue, and the gas phase oil-gas is cooled to obtain light components;

4) vacuum distillation separation

Put the solid phase residue of step 3) into the vacuum distiller for distillation, and cut out the light components with a distillation range<500°C and the heavy components with a distillation range>500°C;

5) Hydrofining

The light components obtained in step 3) are mixed with the <500°C light components distilled in step 4) and then entered into the hydrofinishing reactor, and the hydrofinishing reaction is carried out under the action of a catalyst;

6) Multi-stage vacuum distillation separation

The reaction product of step 5) is separated through a multi-stage distiller to separate naphtha, diesel oil, and VGO, wherein the VGO is returned to the hydrotreating reactor to continue to participate in the reaction.

Further, the process conditions for the above suspended bed hydrocracking reaction are: pressure 20-22MPa, reaction temperature 445-470°C, additive 0-0.75wt%, catalyst 0-1.6wt%, co-catalyst 0-1.0wt%, empty The rate is 0.5-0.7h ^-1 , and the hydrogen consumption is 4-7wt%.

Further, the raw coal in step 1) is one or a mixture of young bituminous coal or lignite.

Further, the additive in step 1) is mainly composed of activated carbon or activated carbon-based active materials, and its specific surface area is 500-600 m ² /g.

Further, the cocatalyst described in step 1) is sodium sulfide or DMDS.

Further, the catalyst described in step 1) and step 2) is xAl ₂ O ₃ ·yFe ₂ O ₃ ·zSiO ₂ ·mTiO ₂ ·nNa ₂ O, and the catalyst is an iron-based catalyst.

Further, in step 2), the cycle gas (6) is preheated hydrogen with a purity of 85-95%.

Further, in step 4), the vacuum distiller (15) may be a wiped film evaporator.

Further, in step 5), the catalyst for the hydrofining reaction is one or more of Al ₂ O ₃ , SiO ₂ , P ₂ O ₅ , SO ₃ , Cl, NiO, MoO ₃ , WO ₃ mixture.

The hydrofinishing described in step 5) is characterized in that sulfur, nitrogen, oxygen, and metals are removed through hydrofinishing reactions; hydrogenation saturation reactions of olefins and aromatics; hydrogenation of alkanes, alkenes, cycloalkanes, and aromatics cracking reaction.

Compared with the prior art, the present invention has the following beneficial effects:

1) The coal concentration in the raw material can reach 35-50%, the reaction temperature range is 445-470°C, the coal conversion rate is >90%, and the liquid yield is >70%, all of which are higher than the existing coal direct liquefaction technology, reaching the level of heavy oil The purpose of improving the utilization of coal and efficient conversion of coal.

2) Compared with the existing direct coal liquefaction technology, this kerosene co-refining technology achieves a high liquid recovery and coal conversion rate with only one reactor, reducing production costs.

3) Using the wiped film evaporator for vacuum distillation technology to realize the separation of oil products and residues, reduce the boiling point of materials, thereby reducing energy consumption and avoiding thermal decomposition of products at high temperatures.

4) Use cheap iron-based catalysts, only add activated carbon additives, and the addition of catalysts and additives is very small, reducing cost investment.

5) The reactor has no internal components, and the gas-liquid-solid three-phase passes through the reactor in a plug-flow manner, and the process is simple.

6) This technology uses a wide range of raw materials, and has low requirements on the properties of raw materials. It can be used for co-refining of kerosene, and can also be used for separate processing of coal and heavy and low-quality oil (atmospheric and vacuum residue, catalytic oil slurry, coal tar, etc.).

7) Due to the full use of the good synergistic effect of coal and FCC oil slurry, the product yield is high, the energy consumption is low, and the product quality is good (it can directly produce diesel blended products with sulfur content meeting Euro IV and Euro V emission standards), liquid High yield and great production flexibility. It has significant economic and environmental benefits.

8) Compared with the direct liquefaction of coal, FCC oil slurry and coal refining oil have less investment per ton of oil, less hydrogen consumption, and higher oil yield.

9) Not affected by heavy metal content, colloid and asphaltene content, nitrogen content and sulfur content in raw materials.

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

Among them: 1—fine coal, 2—catalyst, 3—additive, 4—promoter, 5—FCC oil slurry, 6—cycle gas, 7—hydrogen, 8—naphtha, 9—diesel, 10—VGO, 11 — Raw material preparation, 12 — Heater, 13 — Suspension bed hydrocracking reactor, 14 — Separation unit, 15 — Vacuum distiller, 16 — Hydrofining reactor, 17 — Multistage distiller.

detailed description

The present invention utilizes the method for co-refining oil of FCC oil slurry and coal, comprises the following steps:

1) Preparation of oil-coal slurry

The pulverized coal 1 whose particle size is less than 100 μm is heated and dried until the water content is less than 0.1%, and the qualified coal powder, catalyst 2, additive 3, co-catalyst 4, and FCC oil slurry 5 heated to 100-150°C are passed through the machine The mixer mixes evenly and prepares oil-coal slurry with a solid content of 35-55 wt%. The raw coal is one or a mixture of young bituminous coal or lignite. The additive is composed of activated carbon or activated carbon-based active materials, and its specific surface area is 500-600 m ² /g. The co-catalyst is sodium sulfide or DMDS.

2) Suspension bed hydrocracking

The oil-coal slurry prepared in step 1) is pressurized to 20-23 MPa by the feed high-pressure pump, mixed with circulating gas 6 and hydrogen gas 7 with a purity of 95-99%, and heated to 260-300°C in the heater 12 , entering from the bottom of the suspended bed reactor 13 for hydrocracking reaction; the recycle gas 6 is preheated hydrogen with a purity of 85% to 95%.

The technical conditions of the suspended bed hydrocracking reaction are: pressure 20-22MPa, reaction temperature 445-470°C, additive 0-0.75wt%, catalyst 0-1.6wt%, co-catalyst 0-1.0wt%, space velocity 0.5-0.7 h ^-1 , the hydrogen consumption is 4-7wt%.

3) Gas-liquid separation of hydrocracking products

The reaction product of step 2) enters the separation unit 14 for gas-solid phase separation; the solid phase obtained from the separation is residue, and the gas phase oil-gas is cooled to obtain light components;

4) vacuum distillation separation

The solid phase residue of step 3) enters the vacuum distiller 15 for distillation, and cuts out light components with a distillation range <500°C and heavy components with a distillation range>500°C; the vacuum distiller 15 can be a wiped film evaporator.

5) Hydrofining

The light components obtained in step 3) and the <500°C light components distilled in step 4) are mixed and then enter the hydrofinishing reactor 16, and the hydrofinishing reaction is carried out under the action of a catalyst; the hydrofinishing The catalyst for the reaction is one or a mixture of Al ₂ O ₃ , SiO ₂ , P ₂ O ₅ , SO ₃ , Cl, NiO, MoO ₃ , WO ₃ .

6) Multi-stage vacuum distillation separation

The reaction product in step 5) is then passed through a multi-stage still 17 to separate naphtha 8, diesel oil 9, and VGO 10, wherein the VGO is returned to the hydrotreating reactor 16 to continue to participate in the reaction.

The catalyst described in step 1) and step 2) above is 2Fe ₂ O ₃ ·xAl ₂ O ₃ ·(1-x)CaO·(1+2x)SiO ₂ ·(2-x)TiO ₂ ·(2- 0.5x) Na ₂ O (0≤x≤1), the catalyst is an iron-based catalyst.

The present invention is described in further detail below in conjunction with accompanying drawing:

Referring to Figure 1, heat and dry the pulverized coal 1 that is pulverized to a particle size of less than 100 μm, heat the FCC oil slurry 5 to 100°C, and then dry the coal powder 1, heated oil slurry, catalyst 2, additive 3, and cocatalyst 4 Mix evenly to make oil-coal slurry. After boosting to the required pressure by the feed circulation pump and high-pressure feed pump, mix with the heated circulation gas 6 and hydrogen gas 7, and enter the heater 12 to heat to the required reaction temperature. The suspended bed reactor 13 is used for pyrolysis and hydrogenation reactions at a temperature of 445°C to 470°C.

The hydrocracking reaction product enters the separation unit 14 to separate the gas phase from the oil residue. The oil residue passes through the vacuum distiller 15 to obtain light components and heavy components. Hydrofinishing reactor 16 performs hydrofinishing to remove sulfur, nitrogen, oxygen, and metals; hydrogenation saturation reaction of olefins, aromatics, and condensed ring aromatics; hydrocracking reaction of alkanes, alkenes, cycloalkanes, and aromatics. The product after hydrogenation upgrading passes through multi-stage distiller 17 to separate naphtha 8, diesel oil 9, and VGO 10, wherein VGO returns to the hydrotreating reactor to continue to participate in the reaction.

The present invention is described in further detail below in conjunction with embodiment:

Example 1

Using pure FCC oil slurry as raw material, first mix the oil slurry with catalyst, additives, and co-catalysts, and enter the suspension bed reactor for reaction. Additives are 0-0.75wt%, catalysts are 0-1.6wt%, co-catalysts are 0-1.0wt%, The reaction temperature is 427°C to 462°C. The scale of the device is 150 kg/day, and the process flow is the method of co-refining oil with FCC oil slurry and coal of the present invention.

Example 2

The raw material is Yulin Daliuta coal + FCC oil slurry. First, the Yulin Daliuta coal is pulverized to obtain coal powder with a particle size of less than 100 μm. After drying, it is mixed with heated oil slurry, catalysts, and additives to prepare oil-coal slurry. The additive for the suspended bed hydrocracking reaction is activated carbon, the catalyst is an iron-based catalyst, the additive is 0-0.75wt%, the catalyst is 0-1.6wt%, the co-catalyst is 0-1.0wt%, the reaction temperature is 445 ° C ~ 470 ° C, the co-catalyst The addition amount is 0.5-1.0wt%, the oil-coal slurry concentration is 35-55wt%, the device scale is 150 kg/day, and the process flow is the method of co-refining oil with FCC oil slurry and coal of the present invention.

Example 3

Using FCC oil slurry + atmospheric residual oil as the base oil, and the raw coal is cold water well coal. Firstly, the cold water well coal is pulverized to obtain coal powder with a particle size of less than 100 μm. After drying, it is mixed with heated oil slurry, catalyst, and auxiliary The catalyst and additives are evenly mixed to form oil-coal slurry. The additive for the suspension bed hydrocracking reaction is activated carbon, the catalyst is an iron-based catalyst, the additive is 0-0.75wt%, the catalyst is 0-1.6wt%, and the co-catalyst is 0-1.0wt%. The reaction temperature is 445°C-470°C, the concentration of oil-coal slurry is 35-55%wt, the scale of the device is 150 kg/day, and the process flow is the method of co-refining oil with FCC oil slurry and coal of the present invention.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any form. The claims have pointed out the scope of the present invention. Therefore, within the meaning and scope equivalent to the claims of the present invention Any change should be considered to be included in the scope of the claims.

The basic properties of the FCC oil slurry (FCC) used in Examples 1 to 3 of the present invention are shown in Table 1. The basic properties of the raw coal in Examples 2 and 3 are shown in Table 2, and the results of co-refining of kerosene in Examples 1 to 3 are shown in Table 3.

Table 1 Basic properties of FCC oil slurry

project FCC slurry Density@20℃g/ ^cm3 1.01 Viscosity@80℃mm ² /s 57.24 Asphaltene content wt% 0.17 Solid content wt% 0.14 Kang's charcoal wt% 11.06 Ash wt% 0.20 carbon wt% 89.73 Hydrogen wt% 9.71 H/C atomic ratio 1.30 Sulfur wt% 0.35 Nitrogen wt% 0.42 Oxygen wt% 0.23

Table 2 Basic properties of raw coal

Table 3 Kerosene co-refining results

Claims (7)

1. A method of utilizing FCC oil slurry and coal to refine oil together, is characterized in that, comprises the following steps: 1) Preparation of oil-coal slurry The pulverized coal (1) with a particle size of less than 100 μm is heated and dried until the moisture content is less than 0.1%, and the qualified coal pulverized with the catalyst (2), additive (3), and promoter (4) are heated to 100-150 The FCC oil slurry (5) at ℃ is uniformly mixed by a mechanical mixer to prepare a solid content of 35-55wt% oil-coal slurry; the additive is composed of activated carbon or activated carbon-based active materials, and its specific surface area is 500-600m ² /g; the cocatalyst is sodium sulfide or DMDS; 2) Suspension bed hydrocracking After the oil-coal slurry prepared in step 1) is pressurized to 20-23 MPa by the feed high-pressure pump, it is mixed with circulating gas (6) and hydrogen gas (7) with a purity of 95-99%, and then enters the heater (12) for heating After reaching 260-300°C, it enters from the bottom of the suspension bed reactor (13) for hydrocracking reaction; 3) Gas-liquid separation of hydrocracking products The reaction product of step 2) enters the separation unit (14) for gas-solid phase separation; the solid phase obtained from the separation is residue, and the gas phase oil-gas is cooled to obtain light components; 4) vacuum distillation separation Put the solid phase residue of step 3) into the vacuum distiller (15) for distillation, and cut out the light components with a distillation range<500°C and the heavy components with a distillation range>500°C; 5) Hydrofining After mixing the light components obtained in step 3) and <500°C light components distilled in step 4), they enter the hydrofinishing reactor (16), and carry out a hydrofinishing reaction under the action of a catalyst; 6) Multi-stage vacuum distillation separation The reaction product of step 5) is separated through a multi-stage still (17) to separate naphtha (8), diesel oil (9), and VGO (10), wherein VGO is returned to the hydrotreating reactor (16) to continue to participate in the reaction. 2. A method for co-refining oil using FCC oil slurry and coal according to claim 1, characterized in that the process conditions for the suspension bed hydrocracking reaction are: pressure 20-22MPa, reaction temperature 445-470°C , additive 0-0.75wt%, catalyst 0-1.6wt%, co-catalyst 0-1.0wt%, space velocity 0.5-0.7h ^-1 , hydrogen consumption 4-7wt%. 3. a kind of method utilizing FCC oil slurry and coal to refine oil together according to claim 1, is characterized in that, the raw coal described in step 1) is the mixture of one or both in young bituminous coal or lignite . 4. A method for co-refining oil using FCC oil slurry and coal according to claim 1, characterized in that the catalyst described in step 1) and step 2) is 2Fe ₂ O ₃ ·xAl ₂ O ₃ ·(1-x)CaO·(1+2x)SiO ₂ ·(2-x)TiO ₂ ·(2-0.5x)Na ₂ O (0≤x≤1), the catalyst is an iron-based catalyst. 5. A method for co-refining oil using FCC oil slurry and coal according to claim 1, characterized in that, in step 2), the cycle gas (6) is preheated and has a purity of 85 to 95 % hydrogen. 6. A method for co-refining oil by utilizing FCC oil slurry and coal according to claim 1, characterized in that, in step 4), the vacuum distiller (15) is a wiped film evaporator. 7. A kind of method utilizing FCC oil slurry and coal to refine oil together according to claim 1, is characterized in that, in step 5), the catalyst of described hydrofinishing reaction is Al ₂ O ₃ , SiO ₂ , One or a mixture of P ₂ O ₅ , SO ₃ , Cl, NiO, MoO ₃ , WO ₃ .