CN113122315A - Method for treating ethylene tar and use of carbonyl compound containing olefinic bond - Google Patents
Method for treating ethylene tar and use of carbonyl compound containing olefinic bond Download PDFInfo
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- CN113122315A CN113122315A CN202010040163.8A CN202010040163A CN113122315A CN 113122315 A CN113122315 A CN 113122315A CN 202010040163 A CN202010040163 A CN 202010040163A CN 113122315 A CN113122315 A CN 113122315A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
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Abstract
The invention discloses a method for treating ethylene tar and application of carbonyl compounds containing olefinic bonds. The method comprises the following steps: (1) rectifying ethylene tar, and collecting a fraction with the distillation range of 40-280 ℃ as a rectification fraction; (2) carrying out polymerization reaction on the rectified fraction and carbonyl compound containing olefinic bond in the presence of an initiator to obtain a mixed solution; (3) carrying out solid-liquid separation on the mixed solution to obtain a copolymer resin solid and a mother solution; (4) and distilling the mother liquor to obtain a fraction which can be used as a gasoline component or a diesel component. The method can prepare the copolymer resin from the arene in the ethylene tar through polymerization reaction, can improve the additional value of the ethylene tar, and fully utilizes other fractions.
Description
Technical Field
The invention relates to a method for treating ethylene tar and application of carbonyl compounds containing olefinic bonds.
Background
Ethylene tar is a by-product in ethylene production, and accounts for about 15% of ethylene yield. The ethylene tar is composed of various alkanes, aromatic hydrocarbons, aromatic olefins (including alkene-substituted aromatic hydrocarbons) and heterocyclic compounds containing N, S, O, and has a density (at 20 deg.C) of more than 1.0g/cm3And the impurities such as sulfur, nitrogen and the like are low in content, and the metal impurities are basically not contained. At present, the ethylene tar is mainly used as fuel oil, the overall utilization rate is not high, the economic value is low, and the ethylene tar contains heavy alkenyl arene and the like, so that coking and black smoke are easily generated during combustion, and the environment is polluted.
CN102041091A discloses a method for processing ethylene tar, which is characterized in that the contents of colloid, asphaltene and carbon residue in the ethylene tar are high, the ethylene tar is fractionated into light and heavy fractions, then the light and heavy fractions are treated by a solvent deasphalting method to obtain deasphalted oil and deoiled asphalt, the deasphalted oil and the light fraction of the ethylene tar are mixed and sequentially pass through a hydrogenation protection reaction zone, a hydrogenation refining reaction zone and a hydrocracking reaction zone to obtain gasoline and diesel oil fractions, and the deoiled asphalt is used as a general carbon fiber asphalt raw material. The method improves the added value of the ethylene tar to a certain extent.
CN103102979A discloses a method for producing light fuel oil from ethylene tar. Fractionating ethylene tar into light fraction and heavy fraction, mixing the heavy fraction with conventional coking raw materials, performing delayed coking to obtain coker gasoline, coker diesel oil and coker gas oil, mixing the coker gasoline, the coker diesel oil and the ethylene tar light fraction, performing hydrofining reaction, and distilling the obtained product to obtain gasoline fraction I and fraction heavier than gasoline; and (3) hydrotreating the fraction heavier than gasoline to obtain light fuel oil, distilling to obtain a gasoline fraction II and a diesel oil product, and mixing the gasoline fraction I and the gasoline fraction II to obtain a final gasoline product. The method selects different processing methods aiming at the characteristic of high contents of aromatic hydrocarbon, colloid, carbon residue and asphaltene in the ethylene tar, and improves the added value of the ethylene tar to a certain extent.
CN105038852A discloses a hydrogenation process of ethylene tar, which comprises the following steps: s1, dehydrating and purifying the ethylene tar raw material; s2, fractionating the purified ethylene tar raw material into light fraction and heavy fraction; s3, carrying out partial naphthalene removal treatment on the light fraction in the raw material, and collecting the removed naphthalene product; s4, carrying out slurry bed hydrotreating on heavy fraction in the raw material; s5, fractionating the product obtained after hydrogenation in the S4 slurry bed into a light component, a medium component and a heavy component; mixing the light components with the rest light fraction after naphthalene removal and the light fraction without naphthalene removal in the raw materials, and allowing the mixture to enter a fixed bed for hydrofining; the medium components are circulated to a slurry bed for hydrotreating; the heavy component can be processed to produce carbon material or other products with high added value; s6, rectifying the hydrofined product to obtain naphtha and diesel oil fraction. The process improves the added value of the ethylene tar to a certain extent.
CN109609182A discloses a process for delayed coking of undoped full-fraction ethylene tar, which comprises the following steps: injecting water into preheated ethylene tar, and then heating the ethylene tar in a heating furnace, wherein the temperature of a furnace tube outlet of the heating furnace is 440-470 ℃; and (3) after the heated ethylene tar enters a coking kettle for reaction, entering an atmospheric fractionating tower for distillation and separation to obtain light fraction, petroleum coke and tail oil. The process delays coking of ethylene tar and improves production efficiency to a certain extent.
CN109929589A discloses a method for treating ethylene tar, which comprises the following steps: the preheated ethylene tar enters a pretreatment reactor, contacts with coking reaction effluent from a delayed coking reaction system and reaction effluent from a catalytic cracking reaction system, and is separated to obtain light components and heavy components; the heavy component enters a delayed coking reaction system, and the generated coking reaction effluent enters a pretreatment reactor; the light components and hydrogen enter a hydrogenation reaction system, and the reaction effluent is separated to obtain gas, hydrogenated gasoline fraction, hydrogenated diesel oil fraction and hydrogenated heavy oil fraction; the hydrogenated heavy oil fraction enters a catalytic cracking reaction system, and the reaction effluent directly enters the pretreatment reactor through a second feeding hole of the pretreatment reactor. The treatment method can ensure the stable long-period operation of the whole system and improve the added value of the ethylene tar to a certain extent.
As described above, most patent documents separate and utilize the aromatic hydrocarbons in the ethylene tar by a physicochemical or hydrogenation method, and thus increase the added value of the ethylene tar to some extent, but there are few reports on separating and utilizing the aromatic hydrocarbons in the ethylene tar by a chemical polymerization method.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for processing ethylene tar, which can separate aromatic hydrocarbons from a rectified fraction of ethylene tar through a polymerization reaction to obtain a copolymer resin, and can improve the added value of ethylene tar. Further, no additional solvent may be added to the polymerization reaction system of the present invention. Further, the process of the present invention can distill the mother liquor obtained after the polymerization reaction to obtain a fraction that can be used as a gasoline component or a diesel component. In addition, the invention also provides a step of treating the bottom product of the rectifying tower. It is another object of the present invention to provide a novel use of an ethylenic bond-containing carbonyl compound.
In one aspect, the present invention provides a method for treating ethylene tar, comprising the following steps:
(1) rectifying ethylene tar, and collecting a fraction with the distillation range of 40-280 ℃ as a rectification fraction;
(2) carrying out polymerization reaction on the rectified fraction and carbonyl compound containing olefinic bond in the presence of an initiator to obtain a mixed solution;
(3) carrying out solid-liquid separation on the mixed solution to obtain a copolymer resin solid and a mother solution;
(4) distilling the mother liquor to obtain a fraction which can be used as a gasoline component or a diesel component;
wherein the carbonyl compound containing olefinic bond is selected from maleimide compound shown in formula (1), itaconic anhydride compound shown in formula (2) or maleic anhydride compound shown in formula (3):
in the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1-C3 alkyl group; r3One selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, and an aralkyl group substituted with a group containing a heteroatom selected from N, O or S;
in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group of C1-C5;
in the formula (3), R7And R8Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5.
According to the treatment method, preferably, the rectification is carried out in a rectification tower, the fraction with the distillation range of 40-280 ℃ is collected as rectification fraction, and the bottom product of the rectification tower is collected.
According to the treatment method of the present invention, preferably, in the step (1), a fraction having a distillation range of 40 to 260 ℃ is collected as a rectification fraction.
According to the treatment method of the present invention, preferably, in the step (2), the weight ratio of the rectified fraction to the carbonyl compound containing an ethylenic bond is 1: 0.4-6; the weight ratio of the rectification fraction to the initiator is 1: 0.01-0.5; the polymerization reaction is carried out at 55-155 ℃ for 1.5-10 hours.
According to the treatment method of the present invention, preferably, in formula (1), R1And R2Each independently selected from a hydrogen atom or a methyl group; r3One selected from hydrogen atom, C1-C4 alkyl, cyclohexyl, phenyl and benzyl; in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group of C1-C3; in the formula (3), R7And R8Each independently selected from a hydrogen atom, a methyl group or an ethyl group.
According to the treatment method of the present invention, preferably, in the step (2), the initiator is an azo initiator or an organic peroxide initiator.
According to the treatment method of the present invention, preferably, in the step (2), no additional solvent is added to the polymerization reaction system.
According to the treatment method provided by the invention, preferably, in the step (3), the solid-liquid separation is performed by using a centrifuge, the rotation speed of the centrifuge is 3000-7000 rpm, and the centrifugation time is 2-15 min.
According to the treatment method provided by the invention, preferably, in the step (4), the mother liquor is subjected to atmospheric distillation, and the fraction at the temperature of 40-200 ℃ is collected as a gasoline component and the fraction at the temperature of 200-280 ℃ is collected as a diesel component.
In another aspect, the present invention also provides the use of an olefinic bond-containing carbonyl compound selected from the group consisting of a maleimide-based compound represented by formula (1), an itaconic anhydride-based compound represented by formula (2), and a maleic anhydride-based compound represented by formula (3) in the treatment of an ethylene tar to obtain a gasoline component or a diesel oil component:
in the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1-C3 alkyl group; r3One selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, and an aralkyl group substituted with a group containing a heteroatom selected from N, O or S;
in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group of C1-C5;
in the formula (3), R7And R8Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5.
The invention adopts a chemical polymerization method to treat the arene in the ethylene tar distillation fraction, can obtain the copolymer resin, and can improve the additional value of the ethylene tar. According to the preferred technical scheme of the invention, no additional solvent is added in the polymerization reaction, so that the production cost can be obviously reduced. Further, the method of the present invention can subject the mother liquor obtained after the polymerization reaction to atmospheric distillation to cut a fraction that can be used as a gasoline component or a diesel component. In addition, the method can properly treat the bottom product of the rectifying tower for rectifying the ethylene tar, so that the ethylene tar is fully utilized. The invention expands the application of carbonyl compounds containing olefinic bonds.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Ethylene tar is a byproduct generated in the process of producing ethylene by steam cracking of naphtha and other raw materials. The ethylene tar comprises various alkanes, aromatic hydrocarbons, polycyclic aromatic hydrocarbons without side chains or short side chains, aromatic olefins (including olefin-substituted aromatic hydrocarbons) and heterocyclic compounds containing N, S, O elements. The yield of ethylene tar was about 15% of ethylene. The distillation temperature of 10 wt% of substances in the ethylene tar is about 200 ℃, the distillation temperature of 90 wt% of substances is higher than 600 ℃, and the distillation range distribution is wide. The invention adopts a polymerization reaction method to treat the ethylene tar rectification fraction, thereby preparing the aromatic hydrocarbon in the ethylene tar rectification fraction into the copolymerization resin solid, improving the additional value of the ethylene tar, and adding no extra solvent in the polymerization reaction. In addition, the mother liquor obtained after the polymerization reaction may be distilled to obtain a fraction that can be used as a gasoline component or a diesel component.
The method for treating the aromatic olefin in the ethylene tar comprises the following steps: (1) a rectification step; (2) a polymerization reaction step; (3) a separation step; (4) and (5) mother liquor treatment. Optionally, the method also comprises a treatment step of the bottom product of the rectifying tower. The rectification column bottom product is a rectification fraction obtained by rectifying ethylene tar. As described in detail below.
< rectification step >
In the invention, ethylene tar is rectified, and the fraction with the distillation range of 40-280 ℃ is collected as the rectification fraction. Rectification is a separation process that separates components in a mixture by their different volatility. The rectifying tower is generally composed of a plate rectifying tower and a packed rectifying tower. The present inventors have found that a copolymer resin can be obtained by reacting the fraction having the above distillation range with a carbonyl compound having an ethylenic bond, and the added value of ethylene tar can be improved. In addition, the present invention can perform polymerization without using an additional solvent.
The fraction with the distillation range of 40-280 ℃ can be collected as the rectification fraction. Preferably, the fraction with the distillation range of 40-260 ℃ is collected as the rectification fraction. More preferably, the fraction with the distillation range of 40-230 ℃ is collected as the rectification fraction. The distillation fraction mainly contains various alkanes, alkyl-substituted aromatic hydrocarbons, polycyclic aromatic hydrocarbons, aromatic olefins (including olefin-substituted aromatic hydrocarbons), and the like. The aromatic olefins include styrene, 2, 4-dimethylstyrene, 2, 3-dimethylstyrene, 2, 5-dimethylstyrene, 1-ethyl-1-propenylbenzene, 1-vinyl-2, 3-dihydro-1H-indene, 1, 4-dihydronaphthalene, 1-isopropenylnaphthalene and the like. The alkane includes n-tetradecane, n-pentadecane, n-hexadecane, 9-methyl-nonadecane, 8-methyl-heptadecane, 7-hexyl-tridecane, eicosane, heneicosane, docosane, 10-methyl eicosane, etc. The alkyl-substituted aromatic hydrocarbon includes ethylbenzene, 1-ethyl-2-methylbenzene, 1-ethyl-3-methylbenzene, 2-propylbenzene, 1, 2-diethylbenzene, 1, 3-diethylbenzene, 4-ethyl-1, 2-dimethylbenzene, 2-butylbenzene, 2-methyl-1-propylbenzene, indane and the like. The polycyclic aromatic hydrocarbon includes naphthalene, 1-ethylnaphthalene, 2, 6-dimethylnaphthalene, 2, 3-dimethylnaphthalene, 2, 7-dimethylnaphthalene, 2, 3-dimethylnaphthalene, acenaphthene and the like. This facilitates the next polymerization to obtain the copolymer resin and facilitates further processing of the mother liquor.
The rectification of the invention is carried out at normal pressure. The normal pressure means a pressure close to a standard atmospheric pressure, which slightly varies depending on the geographical environment and the climatic environment.
Collecting the fraction with the distillation range of 40-280 ℃ as a rectification fraction. And the bottom product of the rectifying tower is reserved. As described in detail below.
< polymerization step >
And carrying out polymerization reaction on the rectified fraction and a carbonyl compound containing an olefinic bond in the presence of an initiator to obtain a mixed solution. In the present invention, the polymerization reaction is carried out under the protection of an inert gas. The inert gas may be nitrogen or argon, etc.
The weight ratio of the rectified fraction to the carbonyl compound having an ethylenic bond may be 1:0.4 to 6, preferably 1:0.4 to 3, and more preferably 1:0.5 to 1.5. The weight ratio of the rectification fraction to the initiator may be 1:0.01 to 0.5, preferably 1:0.02 to 0.4, and more preferably 1:0.05 to 0.3. The polymerization reaction can be carried out at 55-155 ℃ for 1.5-10 hours. Preferably, the polymerization reaction is carried out at 55 to 150 ℃ for 1.5 to 9 hours. More preferably, the polymerization is carried out at 60 to 150 ℃ for 2 to 8 hours. This is advantageous in that the aromatic olefin in the ethylene tar can be sufficiently utilized to obtain the copolymer resin. The resulting mixed solution was a mixed solution containing a copolymerized resin solid.
The carbonyl compound containing olefinic bond is selected from maleimide compound, itaconic anhydride compound or maleic anhydride compound. Preferably, the carbonyl compound containing an ethylenic bond is a maleic anhydride-based compound. As described in detail below.
The initiator of the present invention may be an azo initiator or an organic peroxide initiator. The azo initiator may be selected from azobisisobutyronitrile, azobisisoheptonitrile. Preferably, the azo initiator is azobisisobutyronitrile. The organic peroxide initiator is selected from one or more of dibenzoyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, cyclohexanone peroxide and methyl ethyl ketone peroxide. Preferably, the organic peroxide initiator may be one selected from dibenzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate and cumyl peroxyneodecanoate. It was found in the present invention that these initiators can be dispersed directly in the distillate without the need for additional solvents.
The polymerization reaction system of the step (2) may not be added with an additional solvent. Thus being beneficial to reducing the cost and being more environment-friendly. Since the distillation fraction in the range of the distillation range contains a substance capable of dissolving the initiator and the carbonyl compound having an ethylenic bond, the present invention can be made without adding a solvent. The invention skillfully utilizes the characteristic, and no relevant report is provided so far. This is of great significance to commercial production and is not conventional in the art. Of course, the present invention is not limited to the addition of other solvents to the polymerization reaction to allow the reaction to proceed better. Examples of other solvents include, but are not limited to, ethylbenzene, xylene.
The carbonyl compound containing ethylenic bonds being maleic acidImide compound
And carrying out polymerization reaction on the rectified fraction and maleimide compounds in the presence of an initiator to obtain a mixed solution.
The maleimide compound of the invention has a structure shown in a formula (1):
in the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1-C3 alkyl group; r3One selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, and an aralkyl group substituted with a group containing a heteroatom selected from N, O or S.
In the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1 to C3 alkyl group. Examples of C1 to C3 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl. According to one embodiment of the invention, R1And R2Each independently selected from a hydrogen atom and a methyl group.
In the formula (1), R3One selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, and an aralkyl group substituted with a group containing a heteroatom selected from N, O or S. Preferably, R3One selected from hydrogen atom, C1-C4 alkyl, C5-C6 cycloalkyl, C7-C15 aralkyl and C7-C15 alkaryl. More preferably, R3One selected from hydrogen atom, C1-C4 alkyl, cyclohexyl, phenyl and benzyl.
Examples of C1 to C6 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and the like. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of C6 to C20 aralkyl groups include, but are not limited to, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, and the like. Examples of C7-C20 alkaryl include, but are not limited to, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2, 3-dimethylbenzyl, 2, 4-dimethylbenzyl, and the like. Examples of aryl substituted with a group containing a heteroatom selected from N, O or S include, but are not limited to, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, and the like, o-cyanophenyl, m-cyanophenyl, p-cyanophenyl, and the like. Examples of substituted aralkyl groups containing a heteroatom selected from N, O or S include, but are not limited to, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2, 3-dimethoxybenzyl, 2, 4-dimethoxybenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-cyanobenzyl, 3-cyanobenzyl, 4-cyanobenzyl, and the like. The substituent groups have proper volume and small steric hindrance, and are favorable for the polymerization reaction. In addition, the maleimide compounds of these substituents can be directly dissolved in the rectification fraction without adding an additional solvent.
Examples of the maleimide-based compound of the present invention include, but are not limited to, maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-o-nitrophenylmaleimide, N-m-nitrophenylmaleimide, N-t-ethylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-m-methoxyphenylmaleimide, n-p-nitrophenylmaleimide, N-o-cyanophenylmaleimide, N-m-cyanophenylmaleimide, N-p-cyanophenylmaleimide, N-benzylmaleimide, N- (2-methylbenzyl) maleimide, N- (3-methylbenzyl) maleimide, N- (4-methylbenzyl) maleimide, N- (2-methoxybenzyl) maleimide, N- (3-methoxybenzyl) maleimide, N- (4-methoxybenzyl) maleimide, N- (2-nitrobenzyl) maleimide, N- (3-nitrobenzyl) maleimide, N- (4-nitrobenzyl) maleimide, N- (3-cyanobenzyl) maleimide and N- (4-cyanobenzyl) Maleimide, and the like. Preferably, the maleimide-based compound of the present invention is selected from one or more of maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide.
According to a further preferred embodiment of the invention, R1And R2Are each a hydrogen atom; r3One selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
According to a further preferred embodiment of the present invention, the maleimide-based compound of the present invention is one selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide and N-isopropylmaleimide.
For better initiation of the reaction, when the carbonyl compound containing an ethylenic bond is a maleimide compound, the initiator used accordingly is preferably one or more selected from dibenzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate, cumyl peroxyneodecanoate. More preferably, the corresponding initiator is selected from one or more of dibenzoyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate, cumyl peroxyneodecanoate. Still preferably, the corresponding initiator is selected from one of dibenzoyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate, cumyl peroxyneodecanoate.
The carbonyl compound containing olefinic bond is itaconic anhydride compound
And carrying out polymerization reaction on the rectified fraction and an itaconic anhydride compound in the presence of an initiator to obtain a mixed solution.
The itaconic anhydride compound has a structure shown as a formula (2):
in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5. The alkyl group of C1-C5 may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, or neopentyl. According to a particular embodiment of the invention, R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group having from C1 to C3. The alkyl group of C1-C3 may be selected from methyl, ethyl, n-propyl or isopropyl. According to another particular embodiment of the invention, formula (2) is itaconic anhydride. Thus, the polymerization reaction can be smoothly carried out; the reaction raw materials can be directly dissolved in the rectification fraction without adding extra solvent.
Examples of the itaconic anhydride-based compound of the present invention include, but are not limited to, itaconic anhydride, 2-ethylene-succinic anhydride, 2-propylene-succinic anhydride, 3- (propyl-2-alkylene) oxolane-2, 5-dione, 3- (butyl-2-alkylene) oxolane-2, 5-dione, 3- (pentyl-3-alkylene) oxolane-2, 5-dione, 2-methylene-3-methyl-succinic anhydride, 2-methylene-3-ethyl-succinic anhydride, 2-methylene-3-propyl-succinic anhydride, 2-methylene-3-isopropyl-succinic anhydride, 2-methylene-3-butyl-succinic anhydride, 2-propylene-butylene-2-oxide, 2-propylene-2-oxide, 2-butylene-2-, 2-methylene-3-isobutyl-succinic anhydride, 2-methylene-3-tert-butyl-succinic anhydride, 2-ethylene-3-methyl-succinic anhydride, 2-ethylene-3-ethyl-succinic anhydride, 2-ethylene-3-propyl-succinic anhydride, 2-ethylene-3-isopropyl-succinic anhydride, 2-ethylene-3-butyl-succinic anhydride, 2-ethylene-3-isobutyl-succinic anhydride, 2-ethylene-3-tert-butyl-succinic anhydride, 2-propylene-3-methyl-succinic anhydride, 2-propylene-3-ethyl-succinic anhydride, 2-propylene-3-propyl-succinic anhydride, 2-propylene-3-isopropyl-succinic anhydride, 2-propylene-3-butyl-succinic anhydride, 2-propylene-3-isobutyl-succinic anhydride, 2-propylene-3-tert-butyl-succinic anhydride, 3-methyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-propyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-methyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-propyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-methyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (pentyl-2-alkylene) oxolane, and combinations thereof, 3-propyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione and 3-isopropyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione.
For better initiation of the reaction, when the carbonyl compound containing an ethylenic bond is an itaconic anhydride-based compound, the initiator used accordingly may preferably be one or more selected from cyclohexanone peroxide, methyl ethyl ketone peroxide, dibenzoyl peroxide, and tert-butyl peroxybenzoate. More preferably, the initiator is selected from one or more of cyclohexanone peroxide, methyl ethyl ketone peroxide, and tert-butyl peroxybenzoate. Still preferably, the initiator is selected from one of methyl ethyl ketone peroxide and tert-butyl peroxybenzoate.
The carbonyl compound containing olefinic bond is maleic anhydride compound
And carrying out polymerization reaction on the rectified fraction and a maleic anhydride compound in the presence of an initiator to obtain a mixed solution.
The maleic anhydride compound has a structure shown as a formula (3):
in the formula (3), R7And R8Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5. Examples of C1 to C5 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl, and the like. Of these substituentsThe volume is appropriate, the steric hindrance is small, and the smooth operation of the free polymerization reaction can be ensured. In addition, this allows direct dissolution in the rectification fraction without the use of additional solvents. According to one embodiment of the invention, R7And R8Each independently selected from a hydrogen atom, a methyl group or an ethyl group. The invention discovers that the maleic anhydride compounds can be directly dispersed in the distillation fraction, and the polymerization reaction can be carried out without additional solvent.
Examples of the maleic anhydride-based compound of the present invention include, but are not limited to, maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride, diethyl maleic anhydride, di-n-propyl maleic anhydride, diisopropyl maleic anhydride, 1-methyl-2-ethyl maleic anhydride, 1-methyl-2-n-propyl maleic anhydride, 1-methyl-2-isopropyl maleic anhydride, 1-methyl-2-n-butyl maleic anhydride, 1-methyl-2-isobutyl maleic anhydride, 1-methyl-2-tert-butyl maleic anhydride, 1-methyl-2-n-pentyl maleic anhydride, 1-methyl-2-isopentyl maleic anhydride, 1-methyl-2-neopentyl maleic anhydride, 1-ethyl-2-n-propyl maleic anhydride, 1-ethyl-2-isopropyl maleic anhydride, and the like. Preferably, the maleic anhydride compound of the present invention is selected from one or more of maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride and diethyl maleic anhydride. This facilitates the polymerization reaction.
For better initiation of the reaction, when the carbonyl compound containing an ethylenic bond is a maleic anhydride-based compound, the initiator used accordingly is preferably one or more selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate and cumyl peroxyneodecanoate; more preferably one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, lauroyl peroxide, dicetyl peroxydicarbonate and cumyl peroxyneodecanoate.
According to a preferred embodiment of the present invention, the rectified fraction is subjected to a polymerization reaction with a maleic anhydride-based compound in the presence of an initiator to obtain a mixed solution.
< separation step >
And carrying out solid-liquid separation on the mixed solution to obtain a copolymer resin solid and a mother solution. The copolymer resin solid can be directly applied as a chemical raw material. The mother liquor contains various alkanes, aromatic hydrocarbons and the like. The solid-liquid separation method is not particularly limited. However, the present inventors have found that the use of a centrifuge for centrifugation is more suitable for separating the copolymer resin solids from the mother liquor.
According to one embodiment of the invention, the solid-liquid separation is performed by using a centrifuge, the rotation speed of the centrifuge is 3000-7000 rpm, and the centrifugation time is 2-15 min. The rotation speed of the centrifugal machine is preferably 3500 to 6500rpm, and more preferably 4000 to 6000 rpm. The centrifugation time is preferably 3-12 min, and more preferably 5-10 min. This allows for both centrifugal efficiency and clarity of the mother liquor. The mother liquor contains various alkanes and can be further purified.
< step of treating mother liquor >
The treatment of the resulting mother liquor may be carried out with reference to CN106554795A "method for treating ethylene tar", which is incorporated herein in its entirety. Specifically, the obtained mother liquor is distilled by a crude oil distillation device, and gasoline components and diesel components are cut by atmospheric distillation, wherein the gasoline components refer to fractions at 40-200 ℃. The diesel oil component refers to a fraction at 200-280 ℃. The obtained gasoline component and diesel oil component can be respectively used as blending components of common gasoline and common diesel oil.
According to one embodiment of the invention, ethylene tar is rectified at normal pressure, and the fraction at 40-280 ℃ is collected as a rectification fraction; adding 0.4-6 parts by weight of maleimide compounds and 0.01-0.5 part by weight of initiators into 1 part by weight of rectification fraction, and reacting at 55-155 ℃ for 1.5-10 hours under the protection of nitrogen to obtain a mixed solution; and (3) centrifugally separating the mixed solution at 3000-7000 rpm for 2-15 min to obtain a copolymer resin solid and a mother solution. Distilling the mother liquor at normal pressure, collecting fractions at 40-200 ℃ as gasoline components and collecting fractions at 200-280 ℃ as diesel components.
According to another embodiment of the invention, ethylene tar is rectified at normal pressure, and the fraction at 40-280 ℃ is collected as the rectification fraction; adding 0.4-6 parts by weight of itaconic anhydride compounds and 0.01-0.5 part by weight of initiators into 1 part by weight of rectification fraction, and reacting at 55-155 ℃ for 1.5-10 hours under the protection of nitrogen to obtain a mixed solution; and (3) centrifugally separating the mixed solution at 3000-7000 rpm for 2-15 min to obtain a copolymer resin solid and a mother solution. Distilling the mother liquor at normal pressure, collecting fractions at 40-200 ℃ as gasoline components and collecting fractions at 200-280 ℃ as diesel components.
According to another embodiment of the invention, ethylene tar is rectified at normal pressure, and the fraction at 40-280 ℃ is collected as the rectification fraction; adding 0.4-6 parts by weight of maleic anhydride compounds and 0.01-0.5 part by weight of initiators into 1 part by weight of rectification fraction, and reacting at 55-155 ℃ for 1.5-10 hours under the protection of nitrogen to obtain a mixed solution; and carrying out centrifugal separation on the mixed solution at 3000-7000 rpm for 2-15 min to obtain the copolymer resin and the mother solution. Distilling the mother liquor at normal pressure, collecting fractions at 40-200 ℃ as gasoline components and collecting fractions at 200-280 ℃ as diesel components.
According to a preferred embodiment of the invention, ethylene tar is rectified under normal pressure, and the fraction at 40-230 ℃ is collected as a rectified fraction; adding 0.4-3 parts by weight of maleic anhydride compounds and 0.02-0.4 part by weight of initiators into 1 part by weight of rectification fraction, and reacting for 3-9 hours at 60-155 ℃ under the protection of nitrogen to obtain a mixed solution; and carrying out centrifugal separation on the mixed solution at 3500-7000 rpm for 2-10 min to obtain a copolymer resin solid and a mother solution. Distilling the mother liquor at normal pressure, collecting fractions at 40-200 ℃ as gasoline components and collecting fractions at 200-230 ℃ as diesel components.
< treatment step of bottom product of rectifying column >
Rectifying the ethylene tar, collecting the rectification fraction at 40-280 ℃, further processing the bottom product of the rectification tower, and then obtaining the corresponding chemical raw material.
The treatment of the bottom product of the rectification column can be carried out with reference to CN102041091A "method for processing ethylene tar", the entire contents of which are incorporated herein. Specifically, the bottom product of the rectifying tower is fractionated into light fraction and heavy fraction, the cutting point is 400-450 ℃, preferably 400-430 ℃, namely the fraction below 400 ℃ is light fraction, and the fraction above 450 ℃ is heavy fraction. The heavy fraction is deasphalted by a solvent to obtain deasphalted oil and deoiled asphalt, the deasphalted oil is mixed with the light fraction and sequentially passes through a hydrogenation protection reaction zone, a hydrofining reaction zone and a hydrocracking reaction zone, and the obtained hydrocracking product enters a separation system to obtain gasoline and diesel oil fractions.
The hydrorefining reaction zone and the hydrocracking reaction zone preferably adopt a one-stage series process, and the two reaction zones can be in the same reactor or different reactors respectively. The hydrogenation protection reaction zone and the hydrofining reaction zone can be in the same reactor, or a reactor can be adopted before the hydrofining reaction zone.
< use of carbonyl Compound having ethylenic bond >
The present invention has for the first time found that carbonyl compounds containing olefinic bonds can be used for treating ethylene tar to obtain a gasoline component or a diesel component. The present invention therefore provides the use of an olefinic bond-containing carbonyl compound for treating ethylene tar to obtain a gasoline component or a diesel component. Further, the invention provides application of the carbonyl compound containing the olefinic bond in treating ethylene tar distillation fraction with the distillation range of 40-280 ℃ to obtain a gasoline component or a diesel component.
In some embodiments, the ethylene tar is rectified, and the fraction with the distillation range of 40-280 ℃ is collected as the rectification fraction. Preferably, the fraction with the distillation range of 40-260 ℃ is collected as the rectification fraction. More preferably, the fraction with the distillation range of 40-230 ℃ is collected as the rectification fraction. The present inventors have found that, by using the fraction having the above distillation range, the polymerization reaction can be carried out without using an additional solvent. Thus, the added value of the ethylene tar can be improved. The rectification according to the invention is preferably carried out at normal pressure.
The carbonyl compound containing olefinic bond is selected from maleimide compound, itaconic anhydride compound or maleic anhydride compound; preferably maleic anhydride compounds. As described in detail below.
Maleimide compound
The maleimide compound of the present invention is represented by the formula (1):
in the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1-C3 alkyl group; r3One selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, and an aralkyl group substituted with a group containing a heteroatom selected from N, O or S.
In the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1 to C3 alkyl group. Examples of C1 to C3 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl. According to one embodiment of the invention, R1And R2Each independently selected from a hydrogen atom and a methyl group.
In the formula (1), R3One selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, and an aralkyl group substituted with a group containing a heteroatom selected from N, O or S. Preferably, R3One selected from hydrogen atom, C1-C4 alkyl, C5-C6 cycloalkyl, C7-C15 aralkyl and C7-C15 alkaryl. More preferably, R3One selected from hydrogen atom, C1-C4 alkyl, cyclohexyl, phenyl and benzyl.
Examples of C1 to C6 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and the like. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of C6 to C20 aralkyl groups include, but are not limited to, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, and the like. Examples of C7-C20 alkaryl include, but are not limited to, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2, 3-dimethylbenzyl, 2, 4-dimethylbenzyl, and the like. Examples of aryl substituted with a group containing a heteroatom selected from N, O or S include, but are not limited to, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, and the like, o-cyanophenyl, m-cyanophenyl, p-cyanophenyl, and the like. Examples of substituted aralkyl groups containing a heteroatom selected from N, O or S include, but are not limited to, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2, 3-dimethoxybenzyl, 2, 4-dimethoxybenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-cyanobenzyl, 3-cyanobenzyl, 4-cyanobenzyl, and the like. The substituent groups have proper volume and small steric hindrance, and are favorable for the polymerization reaction. In addition, the maleimide compounds of these substituents can be directly dissolved in the rectification fraction without adding an additional solvent.
Examples of the maleimide-based compound of the present invention include, but are not limited to, maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-o-nitrophenylmaleimide, N-m-nitrophenylmaleimide, N-t-ethylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, N-m-methoxyphenylmaleimide, n-p-nitrophenylmaleimide, N-o-cyanophenylmaleimide, N-m-cyanophenylmaleimide, N-p-cyanophenylmaleimide, N-benzylmaleimide, N- (2-methylbenzyl) maleimide, N- (3-methylbenzyl) maleimide, N- (4-methylbenzyl) maleimide, N- (2-methoxybenzyl) maleimide, N- (3-methoxybenzyl) maleimide, N- (4-methoxybenzyl) maleimide, N- (2-nitrobenzyl) maleimide, N- (3-nitrobenzyl) maleimide, N- (4-nitrobenzyl) maleimide, N- (3-cyanobenzyl) maleimide and N- (4-cyanobenzyl) Maleimide, and the like. Preferably, the maleimide-based compound of the present invention is selected from one or more of maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide.
According to a further preferred embodiment of the invention, R1And R2Are each a hydrogen atom; r3One selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
According to a further preferred embodiment of the present invention, the maleimide-based compound of the present invention is one selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide and N-isopropylmaleimide.
Itaconic anhydride compound
The itaconic anhydride compound of the invention is shown as formula (2):
in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5. The alkyl group of C1-C5 may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, or neopentyl. According to a particular embodiment of the invention, R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group having from C1 to C3. The alkyl group of C1-C3 may be selected from methyl, ethyl, n-propyl or isopropyl. According to another particular embodiment of the invention, formula (2) is itaconic anhydride. Thus, the polymerization reaction can be smoothly carried out; the reaction raw materials can be directly reacted without adding extra solventThen dissolved in the distillation fraction.
Examples of the itaconic anhydride-based compound of the present invention include, but are not limited to, itaconic anhydride, 2-ethylene-succinic anhydride, 2-propylene-succinic anhydride, 3- (propyl-2-alkylene) oxolane-2, 5-dione, 3- (butyl-2-alkylene) oxolane-2, 5-dione, 3- (pentyl-3-alkylene) oxolane-2, 5-dione, 2-methylene-3-methyl-succinic anhydride, 2-methylene-3-ethyl-succinic anhydride, 2-methylene-3-propyl-succinic anhydride, 2-methylene-3-isopropyl-succinic anhydride, 2-methylene-3-butyl-succinic anhydride, 2-propylene-butylene-2-oxide, 2-propylene-2-oxide, 2-butylene-2-, 2-methylene-3-isobutyl-succinic anhydride, 2-methylene-3-tert-butyl-succinic anhydride, 2-ethylene-3-methyl-succinic anhydride, 2-ethylene-3-ethyl-succinic anhydride, 2-ethylene-3-propyl-succinic anhydride, 2-ethylene-3-isopropyl-succinic anhydride, 2-ethylene-3-butyl-succinic anhydride, 2-ethylene-3-isobutyl-succinic anhydride, 2-ethylene-3-tert-butyl-succinic anhydride, 2-propylene-3-methyl-succinic anhydride, 2-propylene-3-ethyl-succinic anhydride, 2-propylene-3-propyl-succinic anhydride, 2-propylene-3-isopropyl-succinic anhydride, 2-propylene-3-butyl-succinic anhydride, 2-propylene-3-isobutyl-succinic anhydride, 2-propylene-3-tert-butyl-succinic anhydride, 3-methyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-propyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-methyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-propyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-methyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (pentyl-2-alkylene) oxolane, and combinations thereof, 3-propyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione and 3-isopropyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione.
Maleic anhydride compound
The maleic anhydride compound of the invention is shown as the formula (3):
in the formula (3), R7And R8Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5. Examples of C1 to C5 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl, and the like. The substituent groups have proper volume and small steric hindrance, and can ensure the smooth proceeding of free polymerization reaction. In addition, this allows direct dissolution in the rectification fraction without the use of additional solvents. According to one embodiment of the invention, R7And R8Each independently selected from a hydrogen atom, a methyl group or an ethyl group. The invention discovers that the maleic anhydride compounds can be directly dispersed in the distillation fraction, and the polymerization reaction can be carried out without additional solvent.
Examples of the maleic anhydride-based compound of the present invention include, but are not limited to, maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride, diethyl maleic anhydride, di-n-propyl maleic anhydride, diisopropyl maleic anhydride, 1-methyl-2-ethyl maleic anhydride, 1-methyl-2-n-propyl maleic anhydride, 1-methyl-2-isopropyl maleic anhydride, 1-methyl-2-n-butyl maleic anhydride, 1-methyl-2-isobutyl maleic anhydride, 1-methyl-2-tert-butyl maleic anhydride, 1-methyl-2-n-pentyl maleic anhydride, 1-methyl-2-isopentyl maleic anhydride, 1-methyl-2-neopentyl maleic anhydride, 1-ethyl-2-n-propyl maleic anhydride, 1-ethyl-2-isopropyl maleic anhydride, and the like. Preferably, the maleic anhydride compound of the present invention is selected from one or more of maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride and diethyl maleic anhydride.
Examples 1 to 13
(1) Rectifying the ethylene tar, and collecting a fraction with the distillation range of 40-230 ℃ as a rectification fraction;
(2) adding carbonyl compound containing olefinic bond and initiator into the rectification fraction, and carrying out polymerization reaction under the protection of nitrogen to obtain mixed solution;
(3) carrying out centrifugal separation on the mixed solution at the rotation speed of 4000rpm of a centrifugal machine to obtain a copolymer resin solid and a mother solution;
(4) distilling the mother liquor, collecting fractions at 40-200 ℃ as gasoline components, and collecting fractions at 200-230 ℃ as diesel components.
See table 1 for detailed process parameters.
TABLE 1
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. The method for treating the ethylene tar is characterized by comprising the following steps of:
(1) rectifying ethylene tar, and collecting a fraction with the distillation range of 40-280 ℃ as a rectification fraction;
(2) carrying out polymerization reaction on the rectified fraction and carbonyl compound containing olefinic bond in the presence of an initiator to obtain a mixed solution;
(3) carrying out solid-liquid separation on the mixed solution to obtain a copolymer resin solid and a mother solution;
(4) distilling the mother liquor to obtain a fraction which can be used as a gasoline component or a diesel component;
wherein the carbonyl compound containing olefinic bond is selected from maleimide compound shown in formula (1), itaconic anhydride compound shown in formula (2) or maleic anhydride compound shown in formula (3):
in the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1-C3 alkyl group; r3Selected from hydrogen atom, C1-C6 alkyl, C3-C6 cycloalkyl, C6E, EOne of C20 aralkyl, C7-C20 alkaryl, aryl substituted with a group containing a heteroatom selected from N, O or S, and aralkyl substituted with a group containing a heteroatom selected from N, O or S;
in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group of C1-C5;
in the formula (3), R7And R8Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5.
2. The process according to claim 1, wherein in the step (1), the distillation is carried out in a distillation column, a fraction having a distillation range of 40 to 280 ℃ is collected as a distillation fraction, and a distillation column bottom product is collected.
3. The process according to claim 1, wherein in the step (1), a fraction having a distillation range of 40 to 260 ℃ is collected as the rectification fraction.
4. The process according to claim 1, wherein in the step (2), the weight ratio of the rectified fraction to the carbonyl compound containing an ethylenic bond is 1:0.4 to 6; the weight ratio of the rectification fraction to the initiator is 1: 0.01-0.5; the polymerization reaction is carried out at 55-155 ℃ for 1.5-10 hours.
5. The process according to claim 1, wherein R in the formula (1)1And R2Each independently selected from a hydrogen atom or a methyl group; r3One selected from hydrogen atom, C1-C4 alkyl, cyclohexyl, phenyl and benzyl; in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group of C1-C3; in the formula (3), R7And R8Each independently selected from a hydrogen atom, a methyl group or an ethyl group.
6. The process according to claim 1, wherein in the step (2), the initiator is an azo initiator or an organic peroxide initiator.
7. The process of claim 1, wherein no additional solvent is added to the polymerization system in step (2).
8. The treatment method according to claim 1, wherein in the step (3), the solid-liquid separation is performed by using a centrifuge, the rotation speed of the centrifuge is 3000-7000 rpm, and the centrifugation time is 2-15 min.
9. The process according to any one of claims 1 to 8, wherein in the step (4), the mother liquor is subjected to atmospheric distillation, and a fraction at 40 to 200 ℃ is collected as a gasoline component and a fraction at 200 to 280 ℃ is collected as a diesel component.
10. Use of an olefinic bond-containing carbonyl compound in the treatment of ethylene tar to obtain a gasoline component or a diesel component, characterized in that the olefinic bond-containing carbonyl compound is selected from the group consisting of a maleimide-based compound of formula (1), an itaconic anhydride-based compound of formula (2), or a maleic anhydride-based compound of formula (3):
in the formula (1), R1And R2Each independently selected from a hydrogen atom and a C1-C3 alkyl group; r3Selected from hydrogen atom, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C20 aralkyl, C7-C20 alkaryl, and aryl substituted by a group containing a heteroatom selected from N, O or SOne of an aralkyl group substituted with a group containing a hetero atom selected from N, O or S;
in the formula (2), R4、R5、R6Each independently selected from a hydrogen atom or an alkyl group of C1-C5;
in the formula (3), R7And R8Each independently selected from a hydrogen atom or an alkyl group having from C1 to C5.
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| CN115044392A (en) * | 2022-06-06 | 2022-09-13 | 中建安装集团有限公司 | Process and device for improving comprehensive utilization added value of inferior ethylene cracking tar |
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| CN105949388A (en) * | 2016-05-23 | 2016-09-21 | 北京化工大学 | Functional copolymer directly prepared from higher olefin mixture and preparation method |
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Application publication date: 20210716 |