CN110982553B - Method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenated tail oil fraction - Google Patents
Method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenated tail oil fraction Download PDFInfo
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- 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
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Abstract
A method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenation tail oil fraction comprises the steps of carrying out primary solvent refining on the medium-low temperature coal tar hydrogenation tail oil fraction to obtain primary raffinate oil; under the condition of the presence of a hydrodewaxing and hydrofinishing catalyst, the primary raffinate oil is subjected to a one-stage series hydrodewaxing-hydrofinishing combined process treatment, then is subjected to fractionation to obtain distillate oil with the temperature of more than 320 ℃, and finally is subjected to secondary solvent refining and solvent separation to obtain the coal-based environment-friendly rubber oil. The hydrodewaxing catalyst of the invention selectively cracks the high pour point normal paraffin and the similar normal paraffin in the reactant, supplements the olefin produced in the saturation cracking process of the refined catalyst by hydrogenation, simultaneously carries out partial hydrogenation saturation on the heavy aromatic hydrocarbon component in the raw material, and can convert the heavy aromatic hydrocarbon component into an effective naphthenic base component while reducing the pour point of an oil product, so that the viscosity of the product is reduced slightly, and a higher product yield can be obtained.
Description
Technical Field
The invention belongs to the field of coal tar processing, and particularly relates to a method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenated tail oil fractions.
Background
China has abundant low-temperature coal tar resources, but the utilization rate is low, and the quality-based processing and utilization of the coal tar are hot spots concerned by the industry. The product obtained by hydrogenation of medium-low temperature coal tar can be used as vehicle fuel or chemical raw material. The medium-low temperature coal tar hydrogenated tail oil fraction has low paraffin content and high naphthene and aromatic hydrocarbon content, and can be used for processing and preparing naphthenic base oil chemical products.
The rubber oil is an oil product with softening function used in the rubber synthesis process or in the rubber processing process into products, and the tire rubber oil is the main application field of the rubber oil and has good intermiscibility with rubber. The improvement of environmental requirements is also stricter on the quality requirements of tire rubber oil, wherein the tire rubber oil with excessive polycyclic aromatic hydrocarbon content is prohibited from being used in all aspects in the European Union since 2010, so that the environmental-friendly tire rubber oil is required to be rich in a certain amount of aromatic hydrocarbon and not to exceed the limited polycyclic aromatic hydrocarbon content. The existing high-quality production raw materials of the environment-friendly rubber oil, such as naphthenic oil, have insufficient resources, and most of the rubber oil prepared from other types of raw materials has low intermiscibility with rubber; the coal tar hydrogenation tail oil fraction is rich in cycloparaffins and aromatic hydrocarbons, the raw materials are easy to obtain, and the preparation of the environment-friendly tire rubber oil by processing has great advantages.
Patent CN201610946593.X discloses a method for preparing environment-friendly naphthenic rubber oil from naphthenic vacuum wax oil, which comprises subjecting naphthenic vacuum wax oil to hydrogenation pre-refining, degassing to obtain degassed hydrogenated wax oil, refining the degassed hydrogenated wax oil with solvent, and removing solvent from raffinate to obtain environment-friendly naphthenic rubber oil. The method has the characteristics of high yield and high utilization rate of raw materials, but has the problem of insufficient naphthenic oil resources.
Patent CN201110240555.X adopts a two-stage refining process of ternary composite solvent refining-high pressure hydrofining to treat aromatic extract oil of vacuum distillate oil, so as to prepare environment-friendly rubber oil. The raffinate oil obtained by the ternary composite solvent refining process retains more mono-and bicyclic aromatic hydrocarbons, removes the condensed cyclic aromatic hydrocarbons, and obtains the C of the tire rubber oil productAMore than 16 percent, less than 3 percent of PCA, less than 10mg/kg of 8 PAHs, and more than 74 percent of yield of the environment-friendly rubber oil. The method has the disadvantages of high equipment investment cost and high cost due to the adoption of a high-pressure hydrogenation processThe cost is higher.
In patent CN201710750822.5, crude Olium Triticum oil is used as raw material, and the environmental-friendly rubber oil is prepared by the processes of primary solvent refining, hydrofining, hydro-upgrading and secondary solvent refining, and the environmental-friendly rubber oil C obtained by the processesAThe content is up to 25 percent. However, the yield of the obtained environment-friendly rubber oil product is low due to the adoption of a longer process flow.
Disclosure of Invention
Aiming at the characteristics of insufficient naphthenic oil raw material resources, long production process flow and the like in the production of environment-friendly rubber oil, the invention provides the method for preparing the coal-based environment-friendly rubber oil by adopting the medium-low temperature coal tar hydrogenated tail oil fraction, which has a simple process flow.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenated tail oil fraction comprises the following steps:
(1) carrying out primary solvent refining on the hydrogenation tail oil fraction of the medium-low temperature coal tar, and separating the solvent to obtain primary extract oil and primary raffinate oil;
(2) under the condition of hydrodewaxing and hydrofinishing catalysts, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product;
(3) fractionating the hydrogenation liquid product to obtain distillate oil with the temperature of more than 320 ℃;
(4) and (4) carrying out secondary solvent refining on the distillate oil with the temperature of more than 320 ℃ in the step (3), and separating the solvent to obtain the coal-based environment-friendly rubber oil.
The further improvement of the invention is that in the step (1), the medium and low temperature coal tar hydrogenation tail oil fraction is one or two of medium and low temperature coal tar whole fraction hydrogenation tail oil and medium and low temperature coal tar fraction hydrogenation tail oil.
The further improvement of the invention is that in the step (1), the primary solvent refining is multi-stage countercurrent refining, the stage number is 2-5, and the solvent is one of furfural, phenol and N-methylpyrrolidone;
the mass ratio of the solvent refined by the primary solvent to the medium-low temperature coal tar hydrogenation tail oil fraction is (0.5-4) to 1;
the primary solvent refining temperature is 50-120 ℃.
The method is further improved in that in the step (1), the mass ratio of the solvent refined by the primary solvent to the medium-low temperature coal tar hydrogenated tail oil fraction is (1-3) to 1; the primary solvent refining temperature is 70-90 ℃.
The further improvement of the invention is that in the step (2), when the combined process of pour point depressing and hydrofinishing is carried out on the first-stage series-connection, according to the material flow direction, once-extracted oil passes through a pour point depressing reaction zone and a hydrofinishing reaction zone, a pour point depressing catalyst is filled in the pour point depressing reaction zone, a hydrofinishing catalyst is filled in the hydrofinishing reaction zone, the volume ratio of the pour point depressing catalyst and the hydrofinishing catalyst is (1-5): 1, and the pour point depressing catalyst and the hydrofinishing catalyst are all sulfuration-state catalysts.
The further improvement of the invention is that the volume ratio of the hydrodewaxing catalyst to the hydrofinishing catalyst is (2-4) to 1; the hydrodewaxing catalyst is an FDW-3 catalyst or an RDW-1 catalyst, and the hydrofinishing catalyst is an HTLF-1 catalyst or an FV-5 catalyst.
The further improvement of the invention is that in the step (2), in the combined process of the one-section series hydrodewaxing and hydrofinishing, the reaction temperature of the hydrodewaxing process is 330-380 ℃, the reaction temperature of the hydrofinishing process is 350-380 ℃, when the combined process of the one-section series hydrodewaxing and hydrofinishing is used for treatment, the reaction pressure of the hydrodewaxing reaction area and the hydrofinishing reaction area is 4-16 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the liquid hourly volume airspeed is 0.5h-1～3h-1。
The further improvement of the invention is that the reaction temperature of the hydrodewaxing process is 350-370 ℃;
the reaction temperature of the hydrofinishing process is 350-370 ℃;
the reaction pressure of the hydrodewaxing reaction zone and the hydrofinishing reaction zone is 8 MPa-10 MPa;
the volume ratio of hydrogen to oil is 500: 1-800: 1;
the liquid hourly space velocity is 1.0h-1～2.5h-1。
The further improvement of the invention is that in the step (3), the distillation range of the secondary solvent refining raw material is 320-450 ℃; the temperature for the secondary solvent refining is 70-90 ℃.
The further improvement of the invention is that in the step (4), the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the secondary solvent refining temperature is 50-120 ℃, and the mass ratio of the solvent to distillate oil with the temperature of more than 320 ℃ is (0.5-4): 1; the mass ratio of the solvent to the distillate oil with the temperature of more than 320 ℃ is (1-3) to 1.
Compared with the prior art, the invention has the beneficial effects that: the method takes the low-price medium-low temperature coal tar hydrogenation tail oil fraction as the raw material, and has resource advantages; the environment-friendly rubber oil product is prepared by a combined process of solvent refining, hydrodewaxing, hydrofinishing and solvent refining, a hydrodewaxing reactor and a hydrofinishing reactor are connected in series, hydrogen passes through the process at one time, higher pressure (the hydrogen pressure is not higher than 10MPa) is not required, equipment investment is reduced, the process flow is simple, and the benefit is high; the hydrodewaxing catalyst selectively cracks the high-condensation-point normal paraffin and the similar normal paraffin in reactants, supplements and refines the olefin generated in the saturation cracking process of the catalyst through hydrogenation, simultaneously partially hydrogenates and saturates the heavy aromatic hydrocarbon component in the raw material, and can partially convert the heavy aromatic hydrocarbon component into an effective naphthenic base component while reducing the pour point of an oil product, so that the viscosity of the product is reduced slightly, and a higher product yield can be obtained. The invention not only expands the utilization range of the coal tar, but also ensures the product yield, the prepared rubber oil product meets the requirement of European Union environmental protection standard, the pour point is lower than 6 ℃, and the low-temperature physical property of the rubber product can be improved.
Drawings
FIG. 1 is a flow chart of a preparation method of coal-based environment-friendly rubber oil provided by the invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The specific embodiments of the present invention are provided to illustrate and explain the present invention and not to limit the present invention.
The invention relates to a method for preparing environment-friendly rubber oil by taking coal tar hydrogenation tail oil as a raw material and adopting a combined process of solvent refining, hydrodewaxing, hydrorefining supplement and solvent refining.
Referring to fig. 1, the preparation method of the coal-based environment-friendly rubber oil provided by the invention comprises the following steps:
(1) carrying out primary solvent refining on the hydrogenation tail oil fraction of the medium-low temperature coal tar, and separating the solvent to obtain primary extract oil and primary raffinate oil;
(2) under the condition of hydrodewaxing and hydrofinishing catalysts, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product;
(3) fractionating the hydrogenation liquid product to obtain distillate oil with the temperature of more than 320 ℃ as a raw material for secondary solvent refining;
(4) and (4) carrying out secondary solvent refining on the distillate oil with the temperature of more than 320 ℃ in the step (3), and separating the solvent to obtain secondary raffinate oil, wherein the secondary raffinate oil is the coal-based environment-friendly rubber oil.
In the preparation method, the medium-low temperature coal tar hydrogenated tail oil distillate comprises medium-low temperature coal tar whole distillate hydrogenated tail oil and medium-low temperature coal tar distillate hydrogenated tail oil, and the medium-low temperature coal tar hydrogenated tail oil distillate is one or more of tail oil obtained by hydrotreating, hydrofining and hydrocracking processes.
In the step (1), the primary solvent refining is multi-stage countercurrent refining, the stage number is 2-5, and the solvent is one of furfural (namely 2-furaldehyde), phenol and N-methylpyrrolidone;
in the step (1), the mass ratio of the solvent of the primary solvent refining to the coal tar hydrogenation tail oil fraction is (0.5-4): 1, preferably (1-3): 1;
in the step (1), the primary solvent refining temperature may be 50 to 120 ℃, and preferably 70 to 90 ℃.
In the step (2), according to the material flow direction, the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction area and a hydrofinishing reaction area, namely according to the material flow direction, once raffinate oil passes through the hydrodewaxing reaction area and the hydrofinishing reaction area, and according to the volume ratio of (1-5) to 1, preferably (2-4) to 1, a hydrodewaxing catalyst and a hydrofinishing catalyst are respectively filled, wherein the catalysts are all sulfuration-state catalysts. The hydrodewaxing catalyst is a commercially available FDW-3 catalyst (Changie division of China petrochemical company, Inc.) or an RDW-1 catalyst (Fushun division of China petrochemical company, Inc.), and the hydrofinishing catalyst is a commercially available HTLF-1 catalyst (Liaoning Haitai science and technology development, Inc.) or an FV-5 catalyst (Fushun petrochemical institute of China petrochemical company, Inc.).
In the step (2), in the combined process of the one-section series hydrodewaxing-hydrofinishing, the reaction temperature of the hydrodewaxing process is 330-380 ℃, and preferably 350-370 ℃; the reaction temperature of the hydrofinishing process is 350-380 ℃, and preferably 350-370 ℃;
in the step (2), the reaction pressure of the reaction zone of the one-section series hydrodewaxing-hydrofinishing combined process is 4MPa to 16MPa, and preferably 8MPa to 10 MPa; the volume ratio of the hydrogen to the oil is 300: 1-1000: 1, preferably 500: 1-800: 1; the liquid hourly space velocity is 0.5h-1～3h-1Preferably 1.0h-1～2.5h-1。
In the step (3), the distillation range of the secondary solvent refining raw material (namely distillate oil with the temperature of more than 320 ℃) is 320-450 ℃.
In the step (4), the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the refining temperature of the solvent is 50-120 ℃, and the preferred temperature is 70-90 ℃; the mass ratio of the solvent to the raw materials is (0.5-4): 1, preferably (1-3): 1.
The following are specific examples.
Example 1 preparation of coal-based environmentally friendly rubber oil
Performing three-stage countercurrent refining on low-temperature coal tar full-fraction hydrogenated tail oil serving as a raw material (the properties of the raw material are shown in table 1), wherein a solvent is furfural, the refining temperature is 90 ℃, the mass ratio of the solvent to the raw material is 4:1, and primary raffinate oil is obtained after the solvent is recovered from a product obtained at the top of a refining tower and is used as a raw material for subsequent hydrofining; and recovering the solvent from the product obtained from the bottom of the refining tower to obtain primary extract oil for other purposes.
TABLE 1 Low temperature coal tar whole cut hydrogenated tail oil feedstock Properties
And under the condition of a hydrodewaxing catalyst (FDW-3 catalyst) and a hydrofinishing catalyst (HTLF-1 catalyst), carrying out one-section series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain hydrotreated oil (namely a hydrogenated liquid product).
The one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone, and specifically, a hydrodewaxing catalyst and a hydrofinishing catalyst are respectively filled according to a volume ratio of 4:1 along with the material flow direction, and all the catalysts are sulfided catalysts.
Specifically, the reaction temperature of the hydrodewaxing process is 340 ℃; the reaction temperature of the hydrofinishing process is 360 ℃; the reaction pressure of the reaction zone of the combined process of hydrodewaxing and hydrofinishing is 8MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly space velocity is 2.0h-1。
The obtained hydrogenation liquid product is often distilled under reduced pressure to obtain distillate oil with the temperature of 320-450 ℃ which is used as a raw material for secondary solvent refining.
And carrying out secondary solvent refining on the distillate oil at the temperature of between 320 and 450 ℃, wherein the refining mode is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 80 ℃, and the mass ratio of the solvent to the raw material is 3: 1. And removing the solvent from the obtained secondary raffinate to obtain secondary raffinate oil, namely the coal-based environment-friendly rubber oil.
The performance parameters of the environment-friendly rubber oil prepared in the embodiment are shown in Table 2.
Example 2 preparation of coal-based environmentally friendly rubber oil
Carrying out three-stage countercurrent solvent refining on the same raw materials as in example 1, wherein the solvent is furfural, the refining temperature is 100 ℃, the mass ratio of the solvent to the raw materials is 4:1, and primary raffinate oil is obtained after the solvent is recovered from a product obtained at the top of a refining tower and is used as a raw material for subsequent hydrorefining; the product obtained from the bottom of the refining tower can be used for other purposes after the solvent is recovered to obtain primary extract oil.
And under the condition that a hydrodewaxing catalyst (RDW-1 catalyst) and a hydrofinishing catalyst (FV-5 catalyst) exist, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain the hydrotreated oil.
The one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone, and specifically, a hydrodewaxing catalyst and a hydrofinishing catalyst are respectively filled according to the volume ratio of 3:1 along with the material flow direction, and all the catalysts are sulfided catalysts.
Specifically, the reaction temperature of the hydrodewaxing process is 350 ℃; the reaction temperature of the hydrofinishing process is 370 ℃; the reaction pressure of the reaction zone of the hydrodewaxing-hydrofinishing combined process is 10MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly space velocity is 2.5h-1。
The obtained hydrogenation liquid product is often distilled under reduced pressure to obtain distillate oil with the temperature of 320-450 ℃ which is used as a raw material for secondary solvent refining.
And carrying out secondary solvent refining on the distillate oil at the temperature of between 320 and 450 ℃, wherein the refining mode is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 90 ℃, and the mass ratio of the solvent to the raw material is 3: 1. And removing the solvent from the obtained secondary raffinate to obtain secondary raffinate oil, namely the coal-series environment-friendly rubber oil.
The performance parameters of the environment-friendly rubber oil prepared in the embodiment are shown in Table 2.
Example 3
Carrying out three-stage countercurrent solvent refining on the same raw material as in example 1, wherein the solvent is N-methyl pyrrolidone, the refining temperature is 80 ℃, the mass ratio of the solvent to the raw material is 2:1, and primary raffinate oil is obtained after the solvent is recovered from a product obtained at the top of a refining tower and is used as the raw material for subsequent hydrorefining; and recovering the solvent from the product obtained from the bottom of the refining tower to obtain primary extract oil for other purposes.
And under the condition of a hydrodewaxing catalyst (RDW-1 catalyst) and a hydrofinishing catalyst (FV-5 catalyst), carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain the hydrotreated oil.
The one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone, and specifically, a hydrodewaxing catalyst and a hydrofinishing catalyst are respectively filled according to a volume ratio of 4:1 along with the material flow direction, and all the catalysts are sulfided catalysts.
Specifically, the reaction temperature of the hydrodewaxing process is 340 ℃; the reaction temperature of the hydrofinishing process is 360 ℃; the reaction pressure of the reaction zone of the combined process of hydrodewaxing and hydrofinishing is 8MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly space velocity is 2.0h-1。
The obtained hydrogenation liquid product is often distilled under reduced pressure to obtain distillate oil with the temperature of 320-450 ℃ which is used as a raw material for secondary solvent refining.
And carrying out secondary solvent refining on the distillate oil at the temperature of between 320 and 450 ℃, wherein the refining mode is three-stage countercurrent, the solvent is N-methyl pyrrolidone, the refining temperature of the solvent is 80 ℃, and the mass ratio of the solvent to the raw material is 2: 1. And removing the solvent from the obtained secondary raffinate to obtain secondary raffinate oil, namely the coal-series environment-friendly rubber oil.
The performance parameters of the environment-friendly rubber oil prepared in the embodiment are shown in Table 2.
TABLE 2 Performance parameters of the environmentally friendly rubber oils prepared in examples 1-3
Example 4
(1) Carrying out primary solvent refining on the medium-low temperature coal tar whole fraction hydrogenation tail oil, and separating the solvent to obtain primary extract oil and primary raffinate oil; wherein, the primary solvent refining is multi-stage countercurrent refining, the stage number is 2, and the solvent is furfural;
the mass ratio of the solvent refined by the primary solvent to the coal tar hydrogenation tail oil fraction is 0.5: 1;
the primary solvent refining temperature may be 50 ℃.
(2) Under the condition of hydrodewaxing and hydrofinishing catalysts, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product; wherein, according to the material flow direction, the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone, namely, according to the material flow direction, once raffinate oil passes through the hydrodewaxing reaction zone and the hydrofinishing reaction zone, and is respectively filled with a hydrodewaxing catalyst (FDW-3 catalyst) and a hydrofinishing catalyst (HTLF-1 catalyst) according to the volume ratio of 1:1,
in the one-section series hydrodewaxing-hydrofinishing combined process, the reaction temperature of the hydrodewaxing process is 330 ℃; the reaction temperature of the hydrogenation complementary refining process is 350 ℃;
the reaction pressure of the reaction zone of the one-section series hydrodewaxing-hydrofinishing combined process is 16 MPa; the volume ratio of hydrogen to oil is 300: 1; the liquid hourly space velocity is 0.5h-1。
(3) Fractionating the hydrogenation liquid product to obtain distillate oil with the temperature of more than 320 ℃ as a raw material for secondary solvent refining; wherein the distillation range of the secondary solvent refining raw material is 320-450 ℃.
(4) And (3) carrying out secondary solvent refining on the distillate oil with the temperature of more than 320 ℃ in the step (3), and separating the solvent to obtain secondary raffinate oil, wherein the secondary raffinate oil is the coal-based environment-friendly rubber oil. Wherein the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the refining temperature of the solvent is 120 ℃; the mass ratio of the solvent to the raw materials is 0.5: 1.
example 5
(1) Carrying out primary solvent refining on medium-temperature and low-temperature coal tar distillate hydrogenation tail oil, and separating the solvent to obtain primary extract oil and primary raffinate oil; wherein, the primary solvent refining is multi-stage countercurrent refining, the stage number is 5, and the solvent is phenol;
the mass ratio of the solvent refined by the primary solvent to the coal tar hydrogenation tail oil fraction is 1: 1;
the primary solvent refining temperature may be 120 ℃.
(2) Under the condition of hydrodewaxing and hydrofinishing catalysts, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product; according to the material flow direction, the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction area and a hydrofinishing reaction area, namely, according to the material flow direction, once-extracted oil passes through the hydrodewaxing reaction area and the hydrofinishing reaction area, and a hydrodewaxing catalyst (FDW-3 catalyst) and a hydrofinishing catalyst (HTLF-1 catalyst) are respectively filled according to the volume ratio of 2:1, wherein all the catalysts are sulfide catalysts.
In the one-section series hydrodewaxing-hydrofinishing combined process, the reaction temperature of the hydrodewaxing process is 380 ℃; the reaction temperature of the hydrogenation complementary refining process is 380 ℃;
the reaction pressure of the reaction zone of the first-stage series hydrodewaxing-hydrofinishing combined process is 16 MPa; volume ratio of hydrogen to oilIs 1000: 1; the liquid hourly space velocity is 3h-1。
(3) Fractionating the hydrogenation liquid product to obtain distillate oil with the temperature of more than 320 ℃ as a raw material for secondary solvent refining; wherein the distillation range of the secondary solvent refining raw material is 320-450 ℃.
(4) And (4) carrying out secondary solvent refining on the distillate oil with the temperature of more than 320 ℃ in the step (3), and separating the solvent to obtain secondary raffinate oil, wherein the secondary raffinate oil is the coal-based environment-friendly rubber oil. Wherein the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the refining temperature of the solvent is 50 ℃; the mass ratio of the solvent to the raw materials is 4: 1.
example 6
(1) Carrying out primary solvent refining on the full-fraction hydrogenated tail oil of the medium-low temperature coal tar, and separating the solvent to obtain primary extract oil and primary raffinate oil; wherein, the primary solvent refining is multi-stage countercurrent refining, the stage number is 4, and the solvent is N-methylpyrrolidone;
the mass ratio of the solvent refined by the primary solvent to the coal tar hydrogenation tail oil fraction is 3: 1;
the primary solvent refining temperature may be 70 ℃.
(2) Under the condition of hydrodewaxing and hydrofinishing catalysts, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product; according to the material flow direction, the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone, namely, according to the material flow direction, once-extracted oil passes through the hydrodewaxing reaction zone and the hydrofinishing reaction zone, and a hydrodewaxing catalyst (FDW-3 catalyst) and a hydrofinishing catalyst (HTLF-1 catalyst) are respectively filled according to the volume ratio of 5:1, wherein all the catalysts are sulfided catalysts.
In the one-section series hydrodewaxing-hydrofinishing combined process, the reaction temperature of the hydrodewaxing process is 370 ℃; the reaction temperature of the hydrogenation complementary refining process is 360 ℃;
the reaction pressure of the reaction zone of the one-section series hydrodewaxing-hydrofinishing combined process is 9 MPa; the volume ratio of hydrogen to oil is 500: 1; the liquid hourly space velocity is 1.0h-1。
(3) Fractionating the hydrogenation liquid product to obtain distillate oil with the temperature of more than 320 ℃ as a raw material for secondary solvent refining; wherein the distillation range of the secondary solvent refining raw material is 320-450 ℃.
(4) And (3) carrying out secondary solvent refining on the distillate oil with the temperature of more than 320 ℃ in the step (3), and separating the solvent to obtain secondary raffinate oil, wherein the secondary raffinate oil is the coal-based environment-friendly rubber oil. Wherein the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the refining temperature of the solvent is 70 ℃; the mass ratio of the solvent to the raw materials is 1: 1.
example 7
(1) Carrying out primary solvent refining on the medium-low temperature coal tar whole fraction hydrogenation tail oil, and separating the solvent to obtain primary extract oil and primary raffinate oil; wherein, the primary solvent refining is multi-stage countercurrent refining, the stage number is 3, and the solvent is N-methylpyrrolidone;
the mass ratio of the solvent refined by the primary solvent to the coal tar hydrogenation tail oil fraction is 2: 1;
the primary solvent refining temperature may be 80 ℃.
(2) Under the condition of existence of hydrodewaxing and hydrofinishing catalysts, carrying out one-stage series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product; the combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone according to the material flow direction, namely, once raffinate oil passes through the hydrodewaxing reaction zone and the hydrofinishing reaction zone according to the material flow direction, and a hydrodewaxing catalyst (FDW-3 catalyst) and a hydrofinishing catalyst (HTLF-1 catalyst) are respectively filled according to the volume ratio of 3:1, wherein all the catalysts are sulfided catalysts.
In the one-section series hydrodewaxing-hydrofinishing combined process, the reaction temperature of the hydrodewaxing process is 360 ℃; the reaction temperature of the hydrogenation complementary refining process is 360 ℃;
the reaction pressure of the reaction zone of the one-section series hydrodewaxing-hydrofinishing combined process is 9 MPa; the volume ratio of hydrogen to oil is 700: 1; the liquid hourly space velocity is 1.5h-1。
(3) Fractionating the hydrogenation liquid product to obtain distillate oil with the temperature of more than 320 ℃ as a raw material for secondary solvent refining; wherein the distillation range of the secondary solvent refining raw material is 320-450 ℃.
(4) And (3) carrying out secondary solvent refining on the distillate oil with the temperature of more than 320 ℃ in the step (3), and separating the solvent to obtain secondary raffinate oil, wherein the secondary raffinate oil is the coal-based environment-friendly rubber oil. Wherein the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the refining temperature of the solvent is 85 ℃; the mass ratio of the solvent to the raw materials is 1.5: 1.
the present invention is not limited to the above-described embodiments, and variations and improvements within the object and the scope of the intended effects of the present invention are also included in the contents of the present invention.
Claims (3)
1. A method for preparing coal-based environment-friendly rubber oil by adopting low-temperature coal tar full-fraction hydrogenated tail oil is characterized by comprising the following steps:
taking low-temperature coal tar full-cut hydrogenation tail oil as a raw material, wherein the aromatic hydrocarbon content in the low-temperature coal tar full-cut hydrogenation tail oil is 46.1% by mass, the PCA content in the low-temperature coal tar full-cut hydrogenation tail oil is 9.8% by mass, carrying out three-stage countercurrent refining, wherein the solvent is furfural, the refining temperature is 90 ℃, the mass ratio of the solvent to the raw material is 4:1, and recovering the solvent from a product obtained at the top of a refining tower to obtain primary raffinate oil;
in the presence of an FDW-3 catalyst and an HTLF-1 catalyst, performing one-section series hydrodewaxing-hydrofinishing combined process treatment on the primary raffinate oil to obtain a hydrogenated liquid product;
the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction zone and a hydrofinishing reaction zone, and FDW-3 catalysts and HTLF-1 catalysts are respectively filled according to a volume ratio of 4:1 along with the flow direction of materials, wherein all the catalysts are sulfide catalysts;
the reaction temperature of the hydrodewaxing reaction zone is 340 ℃; the reaction temperature of the hydrofinishing reaction zone is 360 ℃; the reaction pressure of the reaction zone of the combined process of hydrodewaxing and hydrofinishing is 8MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly space velocity is 2.0h-1；
The obtained hydrogenation liquid product is often subjected to reduced pressure distillation to obtain distillate oil with the temperature of 320-450 ℃, and the distillate oil is used as a raw material for secondary solvent refining;
carrying out secondary solvent refining on the distillate oil at the temperature of 320-450 ℃, wherein the refining mode is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 80 ℃, the mass ratio of the solvent to the raw material is 3:1, and the obtained secondary raffinate is subjected to solvent removal to obtain secondary raffinate oil, namely the coal-based environment-friendly rubber oil; the pour point of the coal-based environment-friendly rubber oil is 4 ℃, and the carbon type distribution CAThe content was 15%.
2. A method for preparing coal-based environment-friendly rubber oil by adopting low-temperature coal tar full-fraction hydrogenated tail oil is characterized by comprising the following steps:
taking low-temperature coal tar full-cut hydrogenation tail oil as a raw material, wherein the aromatic hydrocarbon content in the low-temperature coal tar full-cut hydrogenation tail oil is 46.1% by mass, the PCA content in the low-temperature coal tar full-cut hydrogenation tail oil is 9.8% by mass, carrying out three-stage countercurrent solvent refining, wherein the solvent is furfural, the refining temperature is 100 ℃, the mass ratio of the solvent to the raw material is 4:1, and recovering the solvent from a product obtained at the top of a refining tower to obtain primary raffinate oil;
under the condition that an RDW-1 catalyst and an FV-5 catalyst exist, the primary raffinate oil is subjected to a one-stage series hydrodewaxing-hydrofinishing combined process treatment to obtain hydrotreated oil;
the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction area and a hydrofinishing reaction area, and RDW-1 catalysts and FV-5 catalysts are respectively filled according to the volume ratio of 3:1 along with the material flow direction, and all the catalysts are sulfuration-state catalysts;
the critical point of falling to hydrogenThe reaction temperature of the condensation reaction zone is 350 ℃; the reaction temperature of the hydrofinishing reaction zone is 370 ℃; the reaction pressure of the reaction zone of the combined process of hydrodewaxing and hydrofinishing is 10MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly space velocity is 2.5h-1；
The obtained hydrogenation liquid product is subjected to reduced pressure distillation to obtain distillate oil at the temperature of 320-450 ℃, and the distillate oil is used as a raw material for secondary solvent refining;
carrying out secondary solvent refining on the distillate oil at the temperature of 320-450 ℃, wherein the refining mode is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 90 ℃, the mass ratio of the solvent to the raw material is 3:1, and the obtained secondary raffinate is subjected to solvent removal to obtain secondary raffinate oil, namely the coal-based environment-friendly rubber oil; the pour point of the coal-based environment-friendly rubber oil is 3 ℃, and the carbon type distribution CAThe content was 14%.
3. A method for preparing coal-based environment-friendly rubber oil by adopting low-temperature coal tar full-fraction hydrogenated tail oil is characterized by comprising the following steps:
taking low-temperature coal tar full-fraction hydrogenated tail oil as a raw material, wherein the mass content of aromatic hydrocarbon in the low-temperature coal tar full-fraction hydrogenated tail oil is 46.1%, the mass of PCA is 9.8%, carrying out three-stage countercurrent solvent refining, wherein the solvent is N-methyl pyrrolidone, the refining temperature is 80 ℃, the mass ratio of the solvent to the raw material is 2:1, and recovering the solvent from a product obtained at the top of a refining tower to obtain primary raffinate oil;
under the condition of existence of an RDW-1 catalyst and an FV-5 catalyst, the primary raffinate oil is subjected to a one-stage series hydrodewaxing-hydrofinishing combined process treatment to obtain hydrotreated oil;
the one-section series hydrodewaxing-hydrofinishing combined process comprises a hydrodewaxing reaction area and a hydrofinishing reaction area, and RDW-1 catalysts and FV-5 catalysts are respectively filled according to the volume ratio of 4:1 along with the material flow direction, and all the catalysts are sulfuration-state catalysts;
the reaction temperature of the hydrodewaxing reaction zone is 340 ℃; the reaction temperature of the hydrofinishing reaction zone is 360 ℃; the hydrodewaxing-hydrosupplementationThe reaction pressure of the reaction zone of the combined refining process is 8MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly space velocity is 2.0h-1；
The obtained hydrogenation liquid product is subjected to reduced pressure distillation to obtain distillate oil at the temperature of 320-450 ℃, and the distillate oil is used as a raw material for secondary solvent refining;
carrying out secondary solvent refining on the distillate oil at the temperature of 320-450 ℃, wherein the refining mode is three-stage countercurrent, the solvent is N-methyl pyrrolidone, the solvent refining temperature is 80 ℃, the mass ratio of the solvent to the raw material is 2:1, and the obtained secondary raffinate is subjected to solvent removal to obtain secondary raffinate oil, namely the coal-based environment-friendly rubber oil; the pour point of the coal-based environment-friendly rubber oil is 0 ℃, and the carbon type distribution CAThe content was 12%.
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| CN108865257A (en) * | 2017-08-28 | 2018-11-23 | 武汉炼化工程设计有限责任公司 | A kind of production technology of environment-friendly rubber oil |
| CN109722299A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | By the method for coal tar production rubber filling oil |
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| WO2004033596A2 (en) * | 2002-10-08 | 2004-04-22 | Exxonmobil Research And Engineering Company | A method for making lube basestocks |
| CN102585901A (en) * | 2012-02-21 | 2012-07-18 | 中国海洋石油总公司 | Rubber oil with low aromatic hydrocarbon content and preparation method thereof |
| CN104498090A (en) * | 2014-12-17 | 2015-04-08 | 王树宽 | System and method for preparing naphthenic base oil and low freezing point diesel oil through all-hydrogen coal tar |
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