CN116023998A - Method for treating coal tar raw material - Google Patents
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- CN116023998A CN116023998A CN202111243470.7A CN202111243470A CN116023998A CN 116023998 A CN116023998 A CN 116023998A CN 202111243470 A CN202111243470 A CN 202111243470A CN 116023998 A CN116023998 A CN 116023998A
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- 239000011280 coal tar Substances 0.000 title claims abstract description 131
- 239000002994 raw material Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 45
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
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- 238000000746 purification Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 29
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 22
- 229910052708 sodium Inorganic materials 0.000 description 22
- 239000011734 sodium Substances 0.000 description 22
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
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- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for treating coal tar raw materials, which comprises the following steps: (1) The method comprises the steps that a coal tar raw material contacts alkali metal to perform a pre-reaction, wherein the mass content of water in the coal tar raw material is 0.8% -3.2% by taking the weight of coal tar as a reference; (2) Mixing the material subjected to the pre-reaction in the step (1) with alkali metal again for reaction; (3) And (3) carrying out a solid-liquid separation unit on the mixture obtained after the reaction in the step (2) to obtain the final coal tar. The method can solve the problems of complex flow, low liquid yield, high energy consumption, equipment corrosion and the like in the prior art.
Description
Technical Field
The invention belongs to the field of coal chemical industry, relates to a coal tar raw material pretreatment method, and particularly relates to a method for treating full-fraction coal tar raw materials by using an external pretreatment agent.
Background
The coal tar is a liquid product obtained in the carbonization and gasification processes of coal, is a black viscous liquid at normal temperature, mainly comprises polycyclic aromatic compounds, is extremely complex in composition and high in processing difficulty, adopts thermal separation to extract components such as phenol oil, naphthalene and the like, and other components are burnt out in a heavy fuel oil form, so that serious environmental pollution is caused and resource waste is caused.
In recent years, along with the reduction of conventional petroleum resources and the continuous increase of the requirements for clean fuel oil, the preparation of clean fuel oil by coal tar hydrogenation is of great concern, and particularly in the places of Shaanxi, inner Mongolia, xinjiang and the like, the coal tar hydrogenation technology is rapidly developed. Coal tar hydrogenation techniques are broadly divided into: coal tar cutting fraction fixed bed hydrogenation, coal tar full fraction suspended bed/ebullated bed hydrogenation techniques, but whatever the technique, the coal tar needs to be pretreated before being hydrotreated.
The impurity content in the coal tar raw material is high, a large amount of mechanical impurities and moisture can be generated in the carbonization and condensation processes of coal, and the aromatic hydrocarbon content in the coal tar serving as a coal carbonization byproduct is high, particularly the polycyclic aromatic hydrocarbon exists mainly in the form of colloid and asphaltene. The mechanical impurities in the coal tar are mainly coal dust, coke powder, pyrolytic carbon and the like, the particles of the substances are small and high in content, the substances are generally removed by adopting a centrifugal treatment method or a standing sedimentation method and the like, but the removal efficiency is low, especially the particles smaller than 50 mu m are difficult to remove, and the fine particles which are not removed enter a catalyst bed along with a material flow to cause the blockage of the gaps of the bed, so that the pressure drop of the bed is quickly increased, and the running period of the device is shortened. More than 90% of metals in the coal tar raw material are enriched in heavy components of the coal tar, and heavy components carrying a large amount of metals easily form a scale layer on the top of a catalyst bed layer after entering a fixed bed hydrogenation reactor, so that the bed layer is reduced and raised, and on the other hand, the heavy components easily accumulate carbon on the surface of the catalyst to block a catalyst pore channel, so that the catalyst is deactivated. At present, the general pretreatment method for the coal tar full-fraction raw material is to set two types of pre-distillation and delayed coking, and the coal tar raw material is obtained and purified by externally throwing 10% -30% of heavy components or converting the heavy components into low-value coke, but the two pretreatment processes have the problems of high energy consumption, low resource utilization rate and the like. In addition, the coal tar raw material generally contains 3-3% of bright water, and the water can seriously affect the operation stability of the device and the performance of the catalyst, so that the coal tar pretreatment needs to be dehydrated to reduce the water content to below 300 mu g/g-500 mu g/g, and the conventional dehydration has the problems of high energy consumption, high dehydration temperature, easy coal tar coking and the like by adopting normal-pressure dehydration, negative-pressure dehydration and other operations; in addition, naphthenic acid, fatty acid and phenols contained in coal tar raw materials cause corrosion to equipment, and these problems are all needed to be solved in industrial devices.
Patent CN105505453A describes a method for the anhydrous demetallization of coal tar, in particular discloses a method for
A method for desalting and demetallizing coal tar in an anhydrous way. The method sequentially comprises the following steps: heating, mixing the first additive, carrying out first-stage solid-liquid separation, mixing the second additive, and carrying out second-stage solid-liquid separation; the method comprises the steps of adding special auxiliary agents into coal tar containing a large amount of impurities, moderately stirring and mixing the coal tar to enable the impurities to mutually collide and coalesce, and then adopting solid-liquid separation equipment to effectively separate the coal tar in two stages, so that purified coal tar is obtained. The technological process is relatively complex, and the auxiliary agent is mainly acid, so that the loss of heavy components such as asphaltene and the like is caused while metal is removed.
In summary, under the 'dual carbon' goal, how to save energy and reduce consumption, improve the resource utilization rate and reduce the equipment corrosion to the greatest extent in the coal tar pretreatment process needs to be considered, so that it is necessary to develop a novel efficient coal tar full-fraction pretreatment technology, realize coal tar raw material purification while improving the liquid yield, provide high-quality raw materials for downstream processes, and reduce the equipment corrosion.
Disclosure of Invention
Aiming at the problems of complex flow, low liquid yield, high energy consumption, equipment corrosion and the like in the existing coal tar full-fraction raw material pretreatment technology, the invention provides a method for treating coal tar raw materials. The technology of the invention utilizes special auxiliary agents to remove impurities such as metal, water, acidic substances and the like in the coal tar raw materials, improves the liquid yield to the maximum extent, provides high-quality coal tar raw materials for downstream, and realizes the efficient utilization of coal tar resources and the long-period operation of subsequent processing devices.
The invention provides a method for treating coal tar raw materials, which comprises the following steps:
(1) The coal tar raw material is contacted with alkali metal to perform a pre-reaction, wherein the mass content of water in the coal tar raw material is 0.8% -3.2%, preferably 1.0% -2.5%, and more preferably 1.2% -2.0% by taking the weight of the coal tar as a reference;
(2) Mixing the material subjected to the pre-reaction in the step (1) with alkali metal again for reaction;
(3) And (3) carrying out a solid-liquid separation unit on the mixture obtained after the reaction in the step (2) to obtain the final coal tar.
Wherein the mass ratio of the alkali metal used in the step (1) to the alkali metal used in the step (2) is 0.5-10:1, preferably 1-6:1, and more preferably 1.5-5:1.
In the method, the mechanical impurities in the coal tar raw material are 0.05% -0.42%, preferably 0.08% -0.30%, and more preferably 0.10% -0.20%; the mechanical impurities include coke powder, pyrolytic carbon, coal dust, metal oxides such as ferric oxide and the like generated in the pyrolysis process.
In the method, the coal tar in the step (1) is full distillate coal tar, and the full distillate coal tar has the following properties: the density is 0.9800 g-1.0378 g/ml, the sulfur is 2000-5000 mug/g, and the nitrogen is 5000-10000 mug/g.
In the method of the present invention, the alkali metal in the step (1) is one or more than one of Li, na, K, ru, cs, fr.
In the method, the mass ratio of the alkali metal in the step (1) to the coal tar raw material is 0.5-10:100, preferably 1-5:100.
In the method of the present invention, the alkali metal in the step (1) is added to the coal tar raw material in a solid or liquid form under a sealed condition.
In the method of the invention, the alkali metal and the solvent in the step (1) are mixed and then added into the coal tar raw material. The solvent is one or a mixture of a plurality of naphtha, diesel oil, kerosene, wax oil and heavy oil, and can be derived from petroleum-based raw materials or coal-based raw materials. The mixing mass ratio of the solvent to the alkali metal is 2:1-10:1, preferably 3:1-8:1. The reaction effect can be further improved by adopting the scheme of mixing alkali metal with a solvent.
A non-limiting alkali metal and solvent mixing process adopted in the embodiment of the invention is as follows: the alkali metal and the solvent with proper proportion are mixed in the mixing equipment fully and uniformly. The operation condition of stirring in the mixing equipment is that the rotating speed is 600 r/m-3000 r/m, the stirring time is 10 min-60 min, and the temperature of the mixture corresponds to that of the mixture during stirring: 20-150 ℃; preferably, the rotation speed is 1000 r/m-2500 r/m, the stirring time is 15-40 min, and the temperature of the mixture corresponds to the stirring time: 40-110 ℃.
The mixing device can be a static mixer or a tank body containing the static mixer, the static mixer can be one or more of an SV type static mixer, an SX type static mixer, an SL type static mixer, an SH type static mixer and an SK type static mixer, and the static mixer mainly has the function of changing the shape and the sectional area of fluid and simultaneously 'rotating' the fluid so as to achieve the aim of fully mixing different fluids.
In the method, the coal tar raw material and alkali metal are mixed for reaction in the step (1) and can be used as a batch reactor, a continuous reactor, kettle type reaction equipment or tubular type reaction equipment.
In the method of the invention, the reaction operation conditions for mixing the coal tar raw material and alkali metal in the step (1) are as follows: reaction temperature: 80-180 ℃ and hydrogen partial pressure: 1.0-5.0 MPa, reaction time or residence time of 5 min-15 min, hydrogen-oil volume ratio of 50:1-400:1, and preferable operation conditions: reaction temperature: 90-120 ℃, hydrogen partial pressure: 2.0-4.0 MPa, and the reaction time or residence time is 6-12 min, and the hydrogen oil volume ratio is 80:1-200:1.
In the method of the invention, the alkali metal in the step (2) is added into the coal tar after the pre-reaction in the step (1) in a solid or liquid form under a sealing condition.
In the method of the invention, the alkali metal in the step (2) is mixed with the solvent and then added into the coal tar after the pre-reaction in the step (1). The solvent is one or a mixture of a plurality of naphtha, diesel oil, kerosene, wax oil and heavy oil, and can be derived from petroleum-based raw materials or coal-based raw materials. The mixing mass ratio of the solvent to the alkali metal is 2:1-10:1, preferably 3:1-8:1. The reaction effect can be further improved by adopting the scheme of mixing alkali metal with a solvent.
In the method of the invention, the operation conditions for continuously adding alkali metal to carry out the reaction in the step (2) are as follows: reaction temperature: 140-300 ℃, hydrogen partial pressure: 4.0-10.0 MPa, reaction time or residence time of 5 min-60 min, hydrogen-oil volume ratio of 50:1-400:1, and preferable operation conditions: reaction temperature: 180-250 ℃, hydrogen partial pressure: 5.0-8.0 MPa, and the reaction time or residence time is 10-40 min, and the hydrogen oil volume ratio is 80:1-200:1.
In the method, the solid removal in the step (3) utilizes the principle that the density of the solid impurities and the density of the coal tar are different to separate metal sulfides, aggregated mechanical impurities, metal simple substances attached to the metal sulfides, and the like generated by the reaction.
In the step (3), the material solid removal can adopt one or more of centrifugal solid removal, standing sedimentation separation, electric field purification, chemical separation, solvent extraction and cyclone separation; preferably, a mechanical separation method is used, and more preferably, a centrifugal separation method is used.
Compared with the prior art, the method for treating the coal tar raw material has the following advantages:
1. the coal tar raw material of the invention retains proper water, and a proper amount of alkali metal reacts with the water in the coal tar, so that partial active hydrogen is produced as a byproduct while the water is removed, and the hydrogen is uniformly distributed in the material; meanwhile, part of alkaline substances in the byproduct can be subjected to neutralization reaction with acidic substances in the coal tar, so that the pH value of the system is improved, the alkali metal added subsequently can be uniformly dispersed, and the reaction efficiency is improved;
2. the method can efficiently remove the impurities such as metal, S and the like in the coal tar raw material by virtue of higher reactivity of alkali metal, and simultaneously, by utilizing the characteristic of more original mechanical impurities in the coal tar raw material, the existence of the micron-sized coal powder provides a carrier for efficient dispersion of the alkali metal, and metal sulfide and removed metal simple substance generated by the reaction can be attached to the coal powder, so that the deposition on the wall of a reactor is avoided, and convenience is provided for the next solid-liquid separation.
3. The pretreatment technology of the coal tar full-fraction raw material has good purification effect on the coal tar raw material, low impurity removal rate and high liquid yield. The coal tar raw material contains more than 80 percent of sulfur, more than 85 percent of metal, 100 percent of bright water, acidic substances and most of solid particles, wherein the liquid yield is more than 97 percent, and the obtained coal tar raw material has excellent properties and can meet the feeding requirements of hydrogenation devices such as downstream fixed bed hydrogenation, ebullated bed hydrogenation and the like.
4. The technology reduces the removal requirement on water in the coal tar, avoids the problems of coking and high energy consumption of the coal tar caused by high heating temperature in the deep dehydration process of the traditional coal tar pretreatment technology, improves the operation stability of the pretreatment device, and reduces the energy consumption.
Detailed Description
The invention is further described by the following detailed description, but does not limit the scope of the invention. In the context of the present invention, "%" is a percentage of homogeneous mass unless otherwise specified.
The properties of the coal tar raw materials are shown in table 1, the alkali metal is sodium, the solvent is coal-based diesel, and the reaction results are shown in table 2.
In the method for treating the coal tar raw material, the coal tar raw material reacts with alkali metal step by step, the material obtained after the reaction is subjected to liquid-solid separation by a centrifugal machine, the coal tar is finally obtained, the coal tar is used as a downstream deep processing raw material, the solid insoluble is used as a heavy fuel, and the metal in the coal tar is recovered. Solid-liquid treatment is carried out by adopting a three-phase horizontal decanter centrifuge, the rotation speed of the centrifuge is 3000r/m, the centrifugation time is 30min, and the centrifugation temperature is 80 ℃.
Example 1
The method for treating coal tar raw materials is adopted by taking medium-low temperature coal tar corresponding to the embodiment 1 listed in the table 1 as the raw material. Directly adding metal sodium into coal tar raw materials for pre-reaction, wherein the mixing mass ratio of the metal sodium to the coal tar raw materials is 1:100, and the reaction conditions are as follows: reaction temperature: hydrogen partial pressure at 90 ℃): 2.0MPa, reaction time is 6min, and hydrogen-oil volume ratio is 80:1; and (3) continuously adding metal sodium to react after the reaction is finished, wherein the mass ratio of the metal sodium in the step (1) to the metal sodium in the step (2) is 5:1, and the reaction conditions are as follows: reaction temperature: 180 ℃, hydrogen partial pressure: 5.0MPa, reaction time is 10min, and hydrogen-oil volume ratio is 80:1. And centrifuging the reacted materials by adopting a centrifuge to obtain the final coal tar.
Example 2
The method for treating coal tar raw materials is adopted by taking medium-low temperature coal tar corresponding to the example 2 listed in the table 1 as the raw material. Directly adding metal sodium into coal tar raw materials for pre-reaction, wherein the mixing mass ratio of the metal sodium to the coal tar raw materials is 2.5:100, and the reaction conditions are as follows: reaction temperature: 105 ℃, hydrogen partial pressure: 3.0MPa, reaction time is 9min, and hydrogen-oil volume ratio is 140:1; and (3) continuously adding metal sodium to react after the reaction is finished, wherein the mass ratio of the metal sodium in the step (1) to the metal sodium in the step (2) is 3:1, and the reaction conditions are as follows: reaction temperature: 215 ℃, hydrogen partial pressure: 6.5MPa, the reaction time is 25min, and the hydrogen-oil volume ratio is 140:1. And centrifuging the reacted materials by adopting a centrifuge to obtain the final coal tar.
Example 3
The method for treating coal tar raw materials disclosed by the invention is adopted by taking medium-low temperature coal tar corresponding to the example 3 shown in the table 1 as a raw material. Directly adding metal sodium into coal tar raw materials for pre-reaction, wherein the mixing mass ratio of the metal sodium to the coal tar raw materials is 5:100, and the reaction conditions are as follows: reaction temperature: 120 ℃, hydrogen partial pressure: 4.0MPa, the reaction time is 12min, and the hydrogen-oil volume ratio is 200:1; and (3) continuously adding metal sodium to react after the reaction is finished, wherein the mass ratio of the metal sodium in the step (1) to the metal sodium in the step (2) is 1.5:1, and the reaction conditions are as follows: reaction temperature: 250 ℃, hydrogen partial pressure: 8.0MPa, reaction time is 40min, and hydrogen-oil volume ratio is 200:1. And centrifuging the reacted materials by adopting a centrifuge to obtain the final coal tar.
Example 4
The method for treating coal tar raw materials is adopted by taking medium-low temperature coal tar corresponding to the embodiment 1 listed in the table 1 as the raw material. Firstly, mixing metal sodium and coal-based diesel oil in a mixer according to the mass ratio of 1:3, stirring at the speed of 1000r/m for 15min, and stirring at the temperature: and (3) at 40 ℃, obtaining mixed slurry of sodium metal and coal-based diesel. Adding mixed slurry into the coal tar raw material according to the mass ratio of alkali metal to the coal tar raw material of 1:100 for pre-reaction, wherein the reaction conditions are as follows: reaction temperature: hydrogen partial pressure at 90 ℃): 2.0MPa, and the reaction time or the residence time is 6min, and the hydrogen-oil volume ratio is 80:1. Continuously adding the slurry mixture for reaction under the following reaction conditions: reaction temperature: 180 ℃, hydrogen partial pressure: 5.0MPa, reaction time or residence time of 10min, hydrogen oil volume ratio of 80:1, and mass ratio of the metal sodium introduced in the front and the back two times of 5:1. And centrifuging the reacted materials by adopting a centrifuge to obtain the final coal tar.
Example 5
The method for treating coal tar raw materials is adopted by taking medium-low temperature coal tar corresponding to the example 2 listed in the table 1 as the raw material. Firstly, mixing metallic sodium and coal-based diesel oil in a mixer according to the mass ratio of 1:6, stirring at the speed of 1800r/m for 27min, and stirring at the temperature: and (3) at 75 ℃, obtaining mixed slurry of sodium metal and coal-based diesel. Adding mixed slurry into the coal tar raw material according to the mass ratio of alkali metal to the coal tar raw material of 2.5:100 for pre-reaction, wherein the reaction conditions are as follows: reaction temperature: 105 ℃, hydrogen partial pressure: 3.0MPa, reaction time or residence time of 9min, and hydrogen-oil volume ratio of 140:1. Continuously adding the slurry mixture for reaction under the following reaction conditions: reaction temperature: 215 ℃, hydrogen partial pressure: 6.5MPa, the reaction time or the residence time is 25min, the hydrogen oil volume ratio is 140:1, and the mass ratio of the metal sodium introduced in the front and the back is 2.5:1. And centrifuging the reacted materials by adopting a centrifuge to obtain the final coal tar.
Example 6
The method for treating coal tar raw materials disclosed by the invention is adopted by taking medium-low temperature coal tar corresponding to the example 3 shown in the table 1 as a raw material. Firstly, mixing metallic sodium and coal-based diesel oil in a mixer according to the mass ratio of 1:8, stirring at the speed of 2500r/m for 40min, and stirring at the temperature: and (3) at 110 ℃, obtaining mixed slurry of sodium metal and coal-based diesel. Adding mixed slurry into the coal tar raw material according to the mass ratio of alkali metal to the coal tar raw material of 5:100 for pre-reaction, wherein the reaction conditions are as follows: 120 ℃, hydrogen partial pressure: 4.0MPa, the reaction time is 12min, and the hydrogen-oil volume ratio is 200:1; continuously adding the slurry mixture for reaction under the following reaction conditions: reaction temperature: 250 ℃, hydrogen partial pressure: 8.0MPa, reaction time of 40min, hydrogen oil volume ratio of 200:1, and mass ratio of the metal sodium introduced in the front and the back two times of 1.5:1. And centrifuging the reacted materials by adopting a centrifuge to obtain the final coal tar.
Comparative example 1
Substantially the same as in example 1, except that the pretreatment technique described in patent CN201610028928 was used to treat the coal tar whole distillate feedstock. Wherein the raw materials are heated to 150 ℃, the addition amount of the X auxiliary agent is 2500ppm, the dicarboxylic acid accounts for 50 percent, the organic phosphoric acid accounts for 50 percent, and the materials are fully mixed after stirring for 45 minutes; and then carrying out solid-liquid separation, adding 1200ppm of Y auxiliary agent, 60% of glycol polymer and 40% of quaternary ammonium salt, stirring for 20 minutes, and carrying out secondary solid-liquid separation to obtain purified coal tar, wherein the reaction results are shown in Table 2.
Comparative example 2
Substantially the same as in example 1, except that the pretreatment technique described in patent CN201610028928 was used to treat the coal tar whole distillate feedstock. Wherein the raw materials are heated to 150 ℃, the addition amount of the X auxiliary agent is 1500ppm, the dicarboxylic acid accounts for 40 percent, the organic phosphoric acid accounts for 60 percent, and the materials are fully mixed after stirring for 30 minutes; then solid-liquid separation is carried out, 1000ppm of Y auxiliary agent, 60% of glycol polymer and 45% of quaternary ammonium salt are added, stirring is carried out for 20 minutes, secondary solid-liquid separation is carried out, and purified coal tar is obtained, and the reaction results are shown in Table 2.
TABLE 1
TABLE 2
Through the description, the comparative analysis of the examples and the comparative examples, the invention discloses that after the coal tar raw material is treated by the coal tar full-fraction pretreatment technology recommended by the patent of the invention, the coke transportation property of the purified coal treated by the patent of the invention is greatly improved from the aspects of density, carbon residue, asphaltene and water content of the purified coal tar, S, metal content and other impurities, the invention has obvious technical advantages, and the device has longer operation period, thus being an important treatment means for realizing the efficient conversion of unconventional resources such as coal tar and the like.
Claims (12)
1. A method for treating coal tar raw material, which is characterized in that: the method comprises the following steps:
(1) The method comprises the steps that a coal tar raw material contacts alkali metal to perform a pre-reaction, wherein the mass content of water in the coal tar raw material is 0.8% -3.2% by taking the weight of coal tar as a reference;
(2) Mixing the material subjected to the pre-reaction in the step (1) with alkali metal again for reaction;
(3) The mixture obtained after the reaction in the step (2) is subjected to a solid-liquid separation unit to obtain the final coal tar;
wherein the mass ratio of the alkali metal used in the step (1) to the alkali metal used in the step (2) is 0.5-10:1.
2. The method according to claim 1, characterized in that: the mass content of water in the coal tar raw material in the step (1) is 1.0% -2.5% by taking the weight of coal tar as a reference; the mass ratio of the alkali metal used in the step (1) to the alkali metal used in the step (2) is 1-6:1.
3. The method according to claim 2, characterized in that: the method comprises the following steps: the mass content of water in the coal tar raw material in the step (1) is 1.2% -2.0% by taking the weight of coal tar as a reference; the mass ratio of the alkali metal used in the step (1) to the alkali metal used in the step (2) is 1.5-5:1.
4. The method according to claim 1, characterized in that: the mechanical impurities in the coal tar raw material in the step (1) are 0.05-0.42 wt%, preferably 0.08-0.30 wt%, and more preferably 0.10-0.20 wt%.
5. The method according to claim 1, characterized in that: the coal tar in the step (1) is full distillate coal tar, and the full distillate coal tar has the following properties: the density is 0.9800 g-1.0378 g/ml, the sulfur is 2000-5000 mug/g, and the nitrogen is 5000-10000 mug/g.
6. The method according to claim 1, characterized in that: the alkali metal in the step (1) is one or more than one of Li, na, K, ru, cs, fr.
7. The method according to claim 1, characterized in that: the mass ratio of the alkali metal in the step (1) to the coal tar raw material is 0.5-10:100 based on simple substance, and is preferably 1-5:100.
8. The method according to claim 1, characterized in that: in the step (1), alkali metal and a solvent are mixed and then added into the coal tar raw material, wherein the solvent is one or a mixture of naphtha, diesel oil, kerosene, wax oil and heavy oil, and the mixing mass ratio of the solvent to the alkali metal is 2:1-10:1, preferably 3:1-8:1.
9. The method according to claim 1, characterized in that: the reaction operating conditions for mixing the coal tar raw material with alkali metal in the step (1) are as follows: reaction temperature: 80-180 ℃ and hydrogen partial pressure: 1.0-5.0 MPa, reaction time or residence time of 5 min-15 min, hydrogen-oil volume ratio of 50:1-400:1, and preferable operation conditions: reaction temperature: 90-120 ℃, hydrogen partial pressure: 2.0-4.0 MPa, and the reaction time or residence time is 6-12 min, and the hydrogen oil volume ratio is 80:1-200:1.
10. The method according to claim 1, characterized in that: the operation conditions for continuing the reaction with the addition of alkali metal in step (2) are as follows: reaction temperature: 140-300 ℃, hydrogen partial pressure: 4.0-10.0 MPa, and the reaction time or residence time is 5 min-60 min, and the hydrogen oil volume ratio is 50:1-400:1.
11. The method according to claim 1, characterized in that: the operation conditions for continuing the reaction with the addition of alkali metal in step (2) are as follows: reaction temperature: 180-250 ℃, hydrogen partial pressure: 5.0-8.0 MPa, and the reaction time or residence time is 10-40 min, and the hydrogen oil volume ratio is 80:1-200:1.
12. The method according to claim 1, characterized in that: in the step (3), the material is subjected to centrifugal solid removal, standing sedimentation separation, electric field purification, chemical separation, solvent extraction and cyclone separation; preferably, a mechanical separation method is used, and more preferably, a centrifugal separation method is used.
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