CN215480673U - System for preparing degradable plastics by directly liquefying coal to obtain oil product - Google Patents
System for preparing degradable plastics by directly liquefying coal to obtain oil product Download PDFInfo
- Publication number
- CN215480673U CN215480673U CN202121463264.2U CN202121463264U CN215480673U CN 215480673 U CN215480673 U CN 215480673U CN 202121463264 U CN202121463264 U CN 202121463264U CN 215480673 U CN215480673 U CN 215480673U
- Authority
- CN
- China
- Prior art keywords
- unit
- reaction
- oxidation
- communicated
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The utility model relates to the technical field of preparation of degradable plastics, in particular to preparation of degradable oil products by direct coal liquefactionA system of plastic, the system comprising: a fractionating unit for fractionating the liquefied gas directly liquefied by coal to obtain propane and C4Fractionating; the first reaction unit is communicated with the bottom end of the fractionation unit; a reforming unit for reforming naphtha to obtain cyclohexane and C6‑C7Aromatic fraction and C8 +Fractionating; a first oxidation unit in communication with a top end of the reforming unit; a second oxidation unit in communication with a bottom end of the reforming unit; a first polymerization unit in communication with the first reaction unit, the first oxidation unit, and/or the second oxidation unit. The utility model adopts the combination of direct coal liquefaction naphtha and direct coal liquefaction liquefied gas to produce degradable plastics; the comprehensive utilization of the direct liquefied gas and naphtha of the direct coal liquefaction coal is realized, and favorable conditions are provided for the development of the coal-to-liquid industry.
Description
Technical Field
The utility model relates to the technical field of degradable plastic preparation, in particular to a system for preparing degradable plastic by directly liquefying coal to obtain an oil product.
Background
Polyvinyl chloride, polyethylene, polypropylene and other plastics are widely applied to various fields of human daily life, and although the polyvinyl chloride, the polyethylene, the polypropylene and other plastics facilitate human physical life, the used wastes are difficult to degrade under natural conditions and can be completely decomposed generally for decades or even hundreds of years. This not only causes environmental pollution and harms human health, but also affects the normal growth of animals and plants. It is statistical that plastic and polyester products that have been discarded worldwide exceed 70 billion tons, with only 9% being recycled and the others being incinerated, landfilled or otherwise discarded in the environment. With the release of over 4 million tons of fresh material each year, a large amount of new waste is continually being produced. The plastic waste abandoned in the environment has serious potential harm, and is not easy to degrade by natural microorganism bacteria due to stable structure, so that the plastic waste permanently exists and continuously accumulates in the natural environment to pollute soil and water, and finally harms the health of human beings and other organisms.
At present, the industrialization process of degradable materials is rapidly heated. Meanwhile, the treatment of plastic pollution becomes a consensus and unified action, and along with the development of technology, the use of degradable and pollution-free degradable materials gradually becomes an effective way for relieving plastic pollution in various countries in the world. With the gradual improvement of the environmental awareness of consumers, more and more enterprises tend to support the sustainable development mode, and the attention degree of each country to low carbon and environmental protection is higher and higher, the degradable plastics gradually replace some application fields of non-degradable plastics. Under the global plastic-limiting/plastic-prohibiting large environment, the degradable plastic industry faces huge development opportunities in the face of potential replacement markets with the scale of tens of millions of tons.
The direct coal liquefaction technology belongs to a continuous hydrogenation process, mainly produces conventional fuels such as diesel oil, gasoline, aviation kerosene and liquefied gas, and comprehensively utilizes the direct coal liquefaction oil product without further development. The direct coal liquefaction liquefied gas and naphtha mainly take isoparaffin and cycloparaffin as main components, the olefin content is very low, the cycloparaffin content in the naphtha is more than 72 percent, the direct coal liquefaction liquefied gas and naphtha are ideal raw materials for preparing propylene oxide, adipic acid, terephthalic acid and 1, 4-butanediol, and the full industrial chain development of carbon dioxide-based degradable plastics of polypropylene carbonate and poly adipic acid/butylene terephthalate can be realized. The coal-to-liquid process also has the remarkable characteristics of the coal chemical industry process, namely high energy consumption and high carbon dioxide emission, and the development of the coal-to-liquid industry is limited to a certain extent under the current national policy of reducing carbon emission.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the problem of high carbon emission in the direct coal liquefaction technology in the prior art, promote the green and environment-friendly utilization of coal-to-liquid products and provide a system for preparing degradable plastics by directly liquefying coal to form oil products.
In order to achieve the above object, the present invention provides a direct coal liquefaction systemA system for preparing degradable plastics from oil, the system comprising: a fractionating unit for fractionating the liquefied gas directly liquefied by coal to obtain propane and C4Fractionating;
a first reaction unit communicated with the bottom end of the fractionation unit and used for separating C4Carrying out a first reaction on the fraction to obtain 1, 4-butanediol;
a reforming unit for reforming naphtha to obtain cyclohexane and C6-C7Aromatic fraction and C8 +Fractionating;
the first oxidation unit is communicated with the top end of the reforming unit and is used for carrying out first oxidation reaction on cyclohexane to obtain adipic acid;
a second oxidation unit communicated with the bottom end of the reforming unit for passing the C8 +Carrying out a second oxidation reaction on the fraction to obtain terephthalic acid;
the first polymerization unit is communicated with the first reaction unit, the first oxidation unit and/or the second oxidation unit and is used for contacting adipic acid and/or terephthalic acid with 1, 4-butanediol to carry out first polymerization reaction to obtain degradable plastic A;
wherein the degradable plastic A is selected from at least one of polybutylene adipate/terephthalate, polybutylene terephthalate and polybutylene adipate.
Preferably, the system further comprises: an aromatic extraction unit in communication with the reforming unit for extracting C6-C7Aromatic extraction is carried out on the aromatic hydrocarbon fraction to obtain benzene and toluene;
the second reaction unit is communicated with the top of the aromatic extraction unit and is used for carrying out a second reaction on the benzene obtained by aromatic extraction to obtain adipic acid;
the second reaction unit is communicated with the first polymerization unit and is used for introducing adipic acid into the first polymerization unit to carry out the first polymerization reaction.
Preferably, the system further comprises: the aromatic hydrocarbon combination device is communicated with the aromatic hydrocarbon extraction unit and is used for carrying out disproportionation reaction on the toluene to obtain paraxylene and benzene;
the aromatic hydrocarbon combination device is communicated with the second oxidation unit and is used for carrying out a second oxidation reaction on the p-xylene to obtain terephthalic acid;
the top end of the aromatic hydrocarbon combination device is communicated with the second reaction unit and is used for carrying out a second reaction on the benzene obtained by the disproportionation reaction to obtain adipic acid.
Preferably, the first reaction unit includes: a first hydrogenation device for adding the C4Carrying out first hydrogenation on the distillate to obtain n-butane;
the maleic anhydride oxidation device is communicated with the first hydrogenation device and is used for oxidizing n-butane to obtain maleic anhydride;
the hydrolysis device is communicated with the maleic anhydride oxidation device and is used for cooling and hydrolyzing the maleic anhydride to obtain maleic acid;
the second hydrogenation device is communicated with the hydrolysis device and is used for carrying out second hydrogenation on the maleic acid to obtain 1, 4-butanediol;
and the air conveying pipeline is respectively communicated with the first hydrogenation device, the maleic anhydride oxidation device and the second hydrogenation device and is used for conveying air to the first hydrogenation device, the maleic anhydride oxidation device and the second hydrogenation device.
Preferably, the system further comprises: the dehydrogenation unit is communicated with the top end of the fractionation unit and is used for carrying out dehydrogenation reaction on propane to obtain propylene;
the third oxidation unit is communicated with the dehydrogenation unit and is used for carrying out third oxidation reaction on propylene to obtain propylene oxide;
a carbon dioxide delivery unit for delivering carbon dioxide to the system;
and the second polymerization unit is respectively communicated with the third oxidation unit and the carbon dioxide conveying unit and is used for contacting the propylene oxide and the carbon dioxide to carry out a second polymerization reaction to obtain the degradable plastic polypropylene carbonate.
Preferably, the third oxidation unit includes: the propylene oxidation device is used for carrying out third oxidation reaction on propylene to obtain a mixed product;
the pre-separation device is communicated with the propylene oxidation device and is used for pre-separating the mixed product to obtain a crude product, mixed gas and a byproduct;
and the product purification device is communicated with the pre-separation device and is used for purifying the crude product to obtain the refined propylene oxide.
Preferably, the third oxidation unit further comprises: the propylene purification device is communicated with the top end of the pre-separation device and is used for separating the mixed gas to obtain propylene and propane;
the top end of the propylene purification device is communicated with the propylene oxidation device and is used for circularly introducing the separated propylene into the propylene oxidation device.
Preferably, the carbon dioxide delivery unit comprises: the compressors are sequentially communicated and used for boosting and compressing carbon dioxide byproducts generated in the coal-to-liquid production process to obtain compressed carbon dioxide;
a purification device for purifying the compressed carbon dioxide to obtain purified carbon dioxide;
the rectification device is used for rectifying the purified carbon dioxide to obtain high-purity carbon dioxide; and
and the cryogenic device is used for freezing the high-purity carbon dioxide to obtain liquid carbon dioxide.
Preferably, the first polymerization unit includes: the first esterification device is communicated with the first reaction unit, is communicated with the first oxidation unit and/or the second reaction unit, and is used for mixing 1, 4-butanediol and adipic acid to carry out a first esterification reaction to obtain a polymer A;
the second esterification device is respectively communicated with the first reaction unit and the second oxidation unit and is used for mixing 1, 4-butanediol and terephthalic acid to carry out second esterification reaction to obtain a polymer B; and
and the first condensation device is respectively communicated with the first esterification device and the second esterification device and is used for mixing the polymer A and the polymer B to carry out polycondensation reaction to obtain the degradable plastic A.
Preferably, the first polymerization unit comprises a third esterification device which is respectively communicated with the first reaction unit and the second oxidation unit and is used for mixing 1, 4-butanediol and terephthalic acid to carry out a third esterification reaction to obtain a polymer C;
a fourth esterification device which is respectively communicated with the first reaction unit and the third esterification device, is communicated with the first oxidation unit and/or the second reaction unit, and is used for mixing 1, 4-butanediol, the polymer C and adipic acid to perform a fourth esterification reaction to obtain a polymer D;
and the second condensation device is used for carrying out polycondensation reaction on the polymer D to obtain the degradable plastic A.
Preferably, the first polymerization unit comprises a fifth esterification device which is respectively communicated with the first reaction unit, the second oxidation unit and the first oxidation unit and/or the second reaction unit and is used for mixing 1, 4-butanediol, terephthalic acid and adipic acid to carry out a fifth esterification reaction to obtain a polymer E;
and the third condensation device is used for carrying out polycondensation reaction on the polymer E to obtain the degradable plastic A.
Through the technical scheme, the degradable plastic can be produced by directly combining the direct coal liquefied naphtha and the direct coal liquefied gas; the process of producing adipic acid by benzene hydrogenation is reduced, the comprehensive utilization of the direct liquefied coal liquefied gas and naphtha is realized, the development of the coal-to-liquid industry chain to refinement and greenization is promoted, the green and environment-friendly utilization of coal-to-liquid products is promoted, and favorable conditions are provided for the development of the coal-to-liquid industry.
Drawings
FIG. 1 is a system for preparing degradable plastics by direct coal liquefaction of oil according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a first reaction unit according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a third oxidation unit according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of the construction of a carbon dioxide delivery unit according to an embodiment of the present invention;
FIG. 5 is a schematic structural view of a first polymerization unit according to an embodiment of the present invention;
FIG. 6 is a schematic structural view of a first polymerization unit according to an embodiment of the present invention;
fig. 7 is a schematic structural view of a first polymerization unit according to an embodiment of the present invention.
Description of the reference numerals
1. Fractionation unit 2, first reaction unit 3, reforming unit
4. First oxidation unit 5, aromatic hydrocarbon extraction unit 6 and aromatic hydrocarbon combination device
7. A second oxidation unit 8, a second reaction unit 9, a first polymerization unit
10. A dehydrogenation unit 11, a third oxidation unit 12 and a carbon dioxide conveying unit
13. A second polymerization unit 21, a first hydrogenation device 22 and a maleic anhydride oxidation device
23. Hydrolysis device 24, second hydrogenation device 25, and purification device
26. Air transfer line 91, first esterification apparatus 92, second esterification apparatus
93. First condensation device 94, third esterification device 95, fourth esterification device
96. Second condensation apparatus 97, fifth esterification apparatus 98, third condensation apparatus
111. Propylene oxidation device 112, pre-separation device 113 and product purification device
114. Propylene purification device 115, recovery device 121, and compressor
122. Purification device 123, rectification device 124 and cryogenic device
27. Incinerator
Detailed Description
The following detailed description of embodiments of the utility model refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the use of directional terms such as "upper, lower, left, right" generally means upper, lower, left, right as viewed with reference to the accompanying drawings, unless otherwise specified; "inner and outer" generally refer to the inner and outer relative to the profile of the components themselves; "distal and proximal" generally refer to distance relative to the contour of the components themselves.
In the utility model, the main components of the coal direct liquefied gas product are propane and butane, the olefin content is very low, and the product is a high-quality propane dehydrogenation and 1,4 butanediol raw material; refined naphtha produced by the direct coal liquefaction hydrogenation modification device and the Fischer-Tropsch synthesis oil product processing device only contains a small amount of aromatic hydrocarbon, mainly takes normal paraffin, isoparaffin and cycloparaffin as main components, wherein the content of the cycloparaffin reaches more than 72 percent, and the naphtha is a high-quality reforming and aromatic hydrocarbon extraction raw material.
Fig. 1 is a system for preparing degradable plastics by directly liquefying coal to obtain oil according to an embodiment of the present invention, and as shown in fig. 1, the present invention provides a system for preparing degradable plastics by directly liquefying coal to obtain oil, the system comprising: a fractionating unit 1 for fractionating the liquefied gas from direct coal liquefaction to obtain propane and C4Fractionating;
a first reaction unit 2 communicated with the bottom end of the fractionation unit 1 for passing the C4Carrying out a first reaction on the fraction to obtain 1, 4-butanediol;
a reforming unit 3 for reforming naphtha to obtain cyclohexane and C6-C7Aromatic fraction and C8 +Fractionating;
a first oxidation unit 4, which is communicated with the top end of the reforming unit 3 and is used for carrying out a first oxidation reaction on cyclohexane to obtain adipic acid;
a second oxidation unit 7 communicating with a bottom end of the reforming unit 3 for passing the C8 +Fraction is subjected toCarrying out second oxidation reaction to obtain terephthalic acid;
a first polymerization unit 9, which is communicated with the first reaction unit 2, the first oxidation unit 4 and/or the second oxidation unit 7, and is used for contacting adipic acid and/or terephthalic acid with 1, 4-butanediol to perform a first polymerization reaction to obtain a degradable plastic A;
wherein the degradable plastic A is selected from at least one of polybutylene adipate/terephthalate, polybutylene terephthalate and polybutylene adipate.
According to the utility model, in order to make full use of the C obtained by the reforming reaction6-C7To said C6-C7The aromatic fraction of (a) is further processed; preferably, the system further comprises: an aromatic extraction unit 5 in communication with the reforming unit 3 for extracting C6-C7The aromatic hydrocarbon fraction is subjected to aromatic hydrocarbon extraction to obtain benzene and toluene.
According to the utility model, preferably, the system further comprises: and the second reaction unit 8 is communicated with the top of the aromatic hydrocarbon extraction unit 5 and is used for carrying out a second reaction on the benzene obtained by aromatic hydrocarbon extraction to obtain adipic acid.
The process route of the cyclohexane method is as follows: the benzene is subjected to catalytic hydrogenation to obtain cyclohexane, the cyclohexane is oxidized to obtain KA oil (mixed oil of cyclohexanol and cyclohexanone), and then the KA oil is reacted with nitric acid to obtain adipic acid. Further, when the adipic acid is prepared by a cyclohexane method, the second reaction unit 8 comprises sequentially communicated hydrogenation catalytic devices for catalytically hydrogenating benzene to obtain cyclohexane; the catalytic oxidation device is used for carrying out catalytic oxidation on cyclohexane to obtain KA oil; and the second catalytic oxidation device is used for mixing the KA oil and the nitric acid to perform a second catalytic oxidation reaction to obtain the adipic acid.
The cyclohexene method comprises the following process routes: the method comprises the following steps of carrying out partial hydrogenation on benzene to obtain cyclohexene, carrying out water and addition on the cyclohexene to obtain cyclohexanol, and then carrying out reaction on the cyclohexanol and nitric acid to obtain adipic acid. Further, when the adipic acid is prepared by a cyclohexene method, the second reaction unit 8 comprises sequentially communicated partial hydrogenation devices for carrying out catalytic hydrogenation on benzene to obtain cyclohexene; water and an addition device for carrying out addition reaction on cyclohexene to obtain cyclohexanol; and the third catalytic oxidation device is used for mixing cyclohexanol and nitric acid to perform a third catalytic oxidation reaction to obtain adipic acid.
According to the present invention, it is preferred that said second reaction unit 8 is in communication with said first polymerization unit 9 for introducing adipic acid into said first polymerization unit 9 for carrying out said first polymerization reaction.
According to the utility model, the heavy naphtha directly liquefied by coal is subjected to reforming reaction, and the generated aromatic hydrocarbon components rich in benzene, toluene, mixed xylene and the like can be used as raw materials of an aromatic hydrocarbon combination device to produce benzene and p-xylene, and meanwhile, products such as crude aromatic hydrocarbon, heavy aromatic hydrocarbon, hydrogen-containing tail gas, fuel gas and the like are by-produced. Preferably, the system further comprises: and the aromatic hydrocarbon combination device 6 is communicated with the aromatic hydrocarbon extraction unit 5 and is used for carrying out disproportionation reaction on the toluene to obtain paraxylene and benzene.
Further preferably, the aromatic hydrocarbon combination 6 is communicated with the second oxidation unit 7, and is used for carrying out a second oxidation reaction on the p-xylene to obtain terephthalic acid; the process for producing terephthalic acid from para-xylene can be known to those skilled in the art and can be, for example: under the action of a catalyst, acetic acid is used as a solvent, p-xylene is oxidized into crude terephthalic acid through air, and then the crude terephthalic acid is obtained through crystallization, filtration and drying in sequence; the crude terephthalic acid is subjected to hydrofining to remove impurities, and then is crystallized, centrifugally separated and dried to obtain a finished terephthalic acid product.
According to the present invention, preferably, the top of the aromatics complex 6 is connected to the second reaction unit 8 for carrying out a second reaction on the benzene obtained by the disproportionation reaction to obtain adipic acid.
FIG. 2 is a schematic structural view of a first reaction unit according to an embodiment of the present invention; as shown in FIG. 2, in some preferred embodiments of the utility model, theC obtained by fractionating coal direct liquefied gas by using fractionating unit 14The distillate produced 1, 4-butanediol. Preferably, the first reaction unit 2 comprises: a first hydrogenation unit 21 for subjecting the C4Carrying out first hydrogenation on the distillate to obtain n-butane;
a maleic anhydride oxidation device 22 which is communicated with the first hydrogenation device 21 and is used for oxidizing n-butane to obtain maleic anhydride;
the hydrolysis device 23 is communicated with the maleic anhydride oxidation device 22 and is used for cooling and hydrolyzing maleic anhydride to obtain maleic acid;
the second hydrogenation device 24 is communicated with the hydrolysis device 23 and is used for carrying out second hydrogenation on the maleic acid to obtain 1, 4-butanediol;
and an air conveying line 26 which is respectively communicated with the first hydrogenation device 21, the maleic anhydride oxidation device 22 and the second hydrogenation device 24 and is used for conveying air to the first hydrogenation device 21, the maleic anhydride oxidation device 22 and the second hydrogenation device 24.
According to the present invention, the crude product of 1, 4-butanediol obtained by subjecting maleic acid to the second hydrogenation reaction by the second hydrogenation device 24 further contains by-products such as γ -butyrolactone and tetrahydrofuran, and in order to purify the crude product of 1, 4-butanediol, it is preferable that the first reaction unit 2 further includes a purification device 25 for purifying the crude product of 1, 4-butanediol to obtain high purity 1, 4-butanediol, γ -butyrolactone and other by-products. Further preferably, the purifying device 25 is communicated with the second hydrogenation device 24, and is used for circularly introducing the gamma-butyrolactone into the second hydrogenation device 24 for second hydrogenation to obtain the 1, 4-butanediol.
In the present invention, the hydrolysis unit 23, the second hydrogenation unit 24 and the purification unit 25 in the first reaction unit 2 all generate tail gas, which can be introduced into the incinerator 27 for incineration.
In the present invention, C4The process for preparing 1, 4-butanediol by the fraction through the first reaction unit 2 comprises the following steps: under the action of mixed catalyst of vanadium and phosphorus, adding C4The fraction is oxidized to generate maleic anhydride, and then the maleic anhydride is quenched by adding waterObtaining maleic acid, and then carrying out catalytic hydrogenation on the maleic acid to produce 1, 4-butanediol; the process has the advantages of short flow, low investment and less by-products, and can co-produce tetrahydrofuran and gamma-butyrolactone.
The carbon dioxide-based polymer is a high polymer obtained by copolymerizing carbon dioxide and other monomers under the action of a catalyst, and the carbon dioxide-based degradable plastic can be used for disposable packaging materials, disposable medical materials, fresh-keeping materials, mulching films and the like. The used waste only generates carbon dioxide and water during incineration treatment, does not cause secondary pollution to the environment, and can be completely degraded within several months during landfill treatment.
In some preferred embodiments of the present invention, the device provided by the present invention can also be used for preparing degradable plastic polypropylene carbonate (carbon dioxide-based polymer), and preferably, the system further comprises: the dehydrogenation unit 10 is communicated with the top end of the fractionation unit 1 and is used for carrying out dehydrogenation reaction on propane to obtain propylene;
the third oxidation unit 11 is communicated with the dehydrogenation unit 10 and is used for carrying out a third oxidation reaction on propylene to obtain propylene oxide;
a carbon dioxide delivery unit 12 for delivering carbon dioxide to the system;
and the second polymerization unit 13 is respectively communicated with the third oxidation unit 11 and the carbon dioxide conveying unit 12, and is used for contacting the epoxy propane and the carbon dioxide to perform a second polymerization reaction to obtain the degradable plastic polypropylene carbonate.
FIG. 3 is a schematic structural diagram of a third oxidation unit according to an embodiment of the present invention; as shown in figure 3, the method for preparing the propylene oxide by the hydrogen peroxide direct oxidation method only generates the propylene oxide and water, has simple process flow, high product yield and basically no pollution, and belongs to an environment-friendly clean production process. Preferably, the third oxidation unit 11 includes: the propylene oxidation device 111 is used for carrying out a third oxidation reaction on propylene to obtain a mixed product;
the pre-separation device 112 is communicated with the propylene oxidation device 111 and is used for pre-separating the mixed product to obtain a crude product, a mixed gas and a byproduct;
and the product purification device 113 is communicated with the pre-separation device 112 and is used for purifying the crude product to obtain the refined propylene oxide.
Preferably, the third oxidation unit 11 further comprises: a propylene purification device 114, which is communicated with the top end of the pre-separation device 112 and is used for separating the mixed gas to obtain propylene and propane; the top end of the propylene purification device 114 is communicated with the propylene oxidation device 111, and is used for circularly introducing the separated propylene into the propylene oxidation device 111, and introducing the propane into a storage tank for storage.
In the present invention, the by-product contains methanol, water, etc., and the crude product also contains impurities such as methanol and water, and more preferably, the third oxidation unit 11 further includes: and a recovery device 115, which is respectively communicated with the bottom ends of the product purification device 113 and the pre-separation device 112, and is configured to re-separate the byproducts such as methanol and water and the impurities such as methanol and water obtained by separating the crude product to obtain methanol and other impurities, further preferably, the top end of the recovery device 115 is communicated with the propylene oxidation device 111, and is configured to circularly introduce the separated methanol into the propylene oxidation device 111 to mix with propylene for a third oxidation reaction.
In the utility model, the preparation method of the propylene oxide comprises the following steps: in the presence of catalysis, mixing a hydrogen peroxide solution (a mixed solution of methanol and water) and propylene in a propylene oxidation device 111 for third oxidation reaction to obtain a mixed product; then introducing the mixed product into the pre-separation device 112 for pre-separation to obtain a crude product, a mixed gas and a byproduct; introducing the crude product into the product purification device 113 for purification to obtain refined propylene oxide and impurities; introducing the mixed gas into a propylene purification device 114 for separation to obtain propylene and propane, wherein the propylene is circularly introduced into the propylene oxidation device 111, and the propane is introduced into a storage tank for storage; and respectively introducing the by-product and impurities obtained by purifying the crude product into the recovery device 115 for re-separation to obtain methanol and impurities, wherein the methanol is circularly introduced into the propylene oxidation device 111.
FIG. 4 is a schematic diagram of the construction of a carbon dioxide delivery unit according to an embodiment of the present invention; as shown in fig. 4, in some preferred embodiments of the present invention, in order to utilize a carbon dioxide byproduct generated in a coal-to-liquid production process, reduce the emission of carbon dioxide in the coal-to-liquid production process, and promote green environmental utilization of coal-to-liquid products, the carbon dioxide conveying unit 12 includes: the compressors 121 are sequentially communicated and are used for boosting and compressing carbon dioxide byproducts generated in the coal-to-liquid production process to obtain compressed carbon dioxide;
a purification device 122 for purifying the compressed carbon dioxide to obtain purified carbon dioxide;
the rectifying device 123 is configured to rectify the purified carbon dioxide to obtain high-purity carbon dioxide; and
and the cryogenic device 124 is used for freezing the high-purity carbon dioxide to obtain liquid carbon dioxide.
In the utility model, poly adipic acid/butylene terephthalate (PBAT) is biodegradable resin which is prepared by using terephthalic acid, adipic acid and 1, 4-butanediol as main raw materials and performing melt polycondensation after an esterification method. Wherein, the esterification method can be one of co-esterification, partial esterification and series esterification.
FIG. 5 is a schematic structural view of a first polymerization unit according to an embodiment of the present invention; as shown in fig. 5, when PBAT is prepared using a molecular esterification method, the first polymerization unit 9 includes: the first esterification device 91 is communicated with the first reaction unit 2, and the first esterification device 91 is communicated with the first oxidation unit 4 and/or the second reaction unit 8, and is used for mixing 1, 4-butanediol and adipic acid to perform a first esterification reaction to obtain a polymer A;
a second esterification device 92, which is respectively communicated with the first reaction unit 2 and the second oxidation unit 7, and is used for mixing 1, 4-butanediol and terephthalic acid to perform a second esterification reaction to obtain a polymer B; and
and the first condensation device 93 is respectively communicated with the first esterification device 91 and the second esterification device 92, and is used for mixing the polymer A and the polymer B to perform a first polycondensation reaction to obtain the degradable plastic A.
The process for preparing PBAT by the molecular esterification method comprises the following steps: firstly, under the action of a first esterification catalyst, carrying out a first esterification reaction on adipic acid and 1, 4-butanediol in a first esterification device 91 to obtain a polymer A, wherein the temperature of the first esterification reaction is 140-; under the action of a second esterification catalyst, carrying out a second esterification reaction on terephthalic acid and 1, 4-butanediol in a second esterification device 92 to obtain a polymer B, wherein the temperature of the first esterification reaction is 194-220 ℃; then, under the action of a first condensation catalyst, a first polycondensation reaction is carried out on the polymer A and the polymer B in a first condensation device 93 to obtain the degradable plastic A, wherein the conditions of the first polycondensation reaction at least meet the following conditions: the temperature is 240-255 ℃, the time is 80-150min, and the pressure is less than 50 Pa.
FIG. 6 is a schematic structural view of a first polymerization unit according to an embodiment of the present invention; as shown in fig. 6, when PBAT is prepared by a tandem esterification method, the first polymerization unit 9 includes a third esterification apparatus 94, which is respectively communicated with the first reaction unit 2 and the second oxidation unit 7, for mixing 1, 4-butanediol and terephthalic acid to perform a third esterification reaction, to obtain a polymer C;
a fourth esterification apparatus 95, which is respectively communicated with the first reaction unit 2 and the third esterification apparatus 94, and is communicated with the first oxidation unit 4 and/or the second reaction unit 8, and is used for mixing 1, 4-butanediol, polymer C and adipic acid to perform a fourth esterification reaction, so as to obtain a polymer D;
and the second condensation device 96 is used for carrying out polycondensation reaction on the polymer D to obtain the degradable plastic A.
The process for preparing PBAT by the series esterification method comprises the following steps: firstly, under the action of a third esterification catalyst, carrying out a third esterification reaction on terephthalic acid and 1, 4-butanediol in a third esterification device 94 to obtain a polymer C, wherein the temperature of the third esterification reaction is 194-220 ℃; then under the action of a fourth esterification catalyst, mixing 1, 4-butanediol, a polymer C and adipic acid in the fourth esterification device 95 to perform a fourth esterification reaction to obtain a polymer D, wherein the temperature of the fourth esterification reaction is 194-220 ℃; and then carrying out a second polycondensation reaction on the polymer C and the polymer D in a second condensation device 96 under the action of a second condensation catalyst to obtain the degradable plastic A, wherein the conditions of the second polycondensation reaction at least meet the following conditions: the temperature is 240-255 ℃, the time is 80-150min, and the pressure is less than 50 Pa.
FIG. 7 is a schematic structural view of a first polymerization unit according to an embodiment of the present invention; as shown in fig. 7, when PBAT is prepared by a co-esterification method, the first polymerization unit 9 includes a fifth esterification apparatus 97, which is respectively communicated with the first reaction unit 2, the second oxidation unit 7, and the first oxidation unit 4 and/or the second reaction unit 8, and is used for mixing 1, 4-butanediol, terephthalic acid, and adipic acid to perform a fifth esterification reaction, so as to obtain a polymer E;
and the third condensation device 98 is used for carrying out third polycondensation reaction on the polymer E to obtain the degradable plastic A.
The process for preparing PBAT by the co-esterification method comprises the following steps: firstly, under the action of a fifth esterification catalyst, carrying out a fifth esterification reaction on terephthalic acid, 1, 4-butanediol and adipic acid in a fifth esterification device 97 to obtain a polymer E, wherein the temperature of the fifth esterification reaction is 160-220 ℃; and then, under the action of a third condensation catalyst, performing a third polycondensation reaction on the polymer E in a second condensation device 98 to obtain the degradable plastic A, wherein the conditions of the third polycondensation reaction at least meet the following conditions: the temperature is 240-255 ℃, the time is 80-150min, and the pressure is less than 50 Pa.
According to the utility model, the special performance different from petroleum-based oil products is endowed with the direct liquefaction product according to the specific annular molecular structure, the direct liquefaction product can be used for deep processing of the components of the direct coal liquefaction liquefied gas and the naphtha to produce the degradable plastics, the integrated construction and operation of the product can be realized, and the direct liquefaction product has important significance for prolonging the industrial chain of the direct liquefaction project; the system provided by the utility model can reduce the procedure of producing adipic acid by benzene hydrogenation, realizes comprehensive utilization of direct liquefied coal and liquefied gas and naphtha, promotes development of coal-to-oil industry chain to refinement and greening, accords with national policies of white pollution treatment and degradable material industry development, and has important significance for environmental protection and carbon neutralization.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the utility model, numerous simple modifications can be made to the technical solution of the utility model, including combinations of the individual specific technical features in any suitable way. The utility model is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (11)
1. A system for preparing degradable plastics by directly liquefying coal to obtain oil products is characterized by comprising: a fractionation unit (1) for fractionating the liquefied gas from direct coal liquefaction to obtain propane and C4Fractionating;
a first reaction unit (2) in communication with the bottom end of the fractionation unit (1) for reacting C4Carrying out a first reaction on the fraction to obtain 1, 4-butanediol;
a reforming unit (3) for reforming naphtha to obtain cyclohexane and C6-C7Aromatic fraction and C8 +Fractionating;
a first oxidation unit (4) which is communicated with the top end of the reforming unit (3) and is used for carrying out a first oxidation reaction on cyclohexane to obtain adipic acid;
a second oxidation unit (7) communicating with the bottom end of the reforming unit (3) for passing the C8 +Carrying out a second oxidation reaction on the fraction to obtain terephthalic acid;
a first polymerization unit (9) which is communicated with the first reaction unit (2), the first oxidation unit (4) and/or the second oxidation unit (7) and is used for contacting adipic acid and/or terephthalic acid with 1, 4-butanediol to carry out a first polymerization reaction to obtain degradable plastic A;
wherein the degradable plastic A is selected from at least one of polybutylene adipate/terephthalate, polybutylene terephthalate and polybutylene adipate.
2. The system of claim 1, further comprising: an aromatics extraction unit (5) in communication with the reforming unit (3) for extracting C6-C7Aromatic extraction is carried out on the aromatic hydrocarbon fraction to obtain benzene and toluene;
the second reaction unit (8) is communicated with the top of the aromatic extraction unit (5) and is used for carrying out a second reaction on the benzene obtained by aromatic extraction to obtain adipic acid;
the second reaction unit (8) is communicated with the first polymerization unit (9) and is used for introducing adipic acid into the first polymerization unit (9) to carry out the first polymerization reaction.
3. The system of claim 2, further comprising: the aromatic hydrocarbon combination device (6) is communicated with the aromatic hydrocarbon extraction unit (5) and is used for carrying out disproportionation reaction on the toluene to obtain p-xylene and benzene;
the aromatic hydrocarbon combination device (6) is communicated with the second oxidation unit (7) and is used for carrying out a second oxidation reaction on p-xylene to obtain terephthalic acid;
the top end of the aromatic hydrocarbon combination device (6) is communicated with the second reaction unit (8) and is used for carrying out a second reaction on the benzene obtained by the disproportionation reaction to obtain adipic acid.
4. The system according to claim 1, characterized in that the first reaction unit (2) comprises: a first hydrogenation unit (21) for adding the C4Carrying out first hydrogenation on the distillate to obtain n-butane;
a maleic anhydride oxidation device (22) which is communicated with the first hydrogenation device (21) and is used for oxidizing n-butane to obtain maleic anhydride;
the hydrolysis device (23) is communicated with the maleic anhydride oxidation device (22) and is used for cooling and hydrolyzing maleic anhydride to obtain maleic acid;
the second hydrogenation device (24) is communicated with the hydrolysis device (23) and is used for carrying out second hydrogenation on the maleic acid to obtain 1, 4-butanediol;
and the air conveying pipeline (26) is respectively communicated with the first hydrogenation device (21), the maleic anhydride oxidation device (22) and the second hydrogenation device (24) and is used for conveying air to the first hydrogenation device (21), the maleic anhydride oxidation device (22) and the second hydrogenation device (24).
5. The system of any one of claims 1-4, further comprising: the dehydrogenation unit (10) is communicated with the top end of the fractionation unit (1) and is used for carrying out dehydrogenation reaction on propane to obtain propylene;
the third oxidation unit (11) is communicated with the dehydrogenation unit (10) and is used for carrying out third oxidation reaction on propylene to obtain propylene oxide;
a carbon dioxide delivery unit (12) for delivering carbon dioxide to the system;
and the second polymerization unit (13) is respectively communicated with the third oxidation unit (11) and the carbon dioxide conveying unit (12) and is used for contacting propylene oxide and carbon dioxide to carry out a second polymerization reaction to obtain the degradable plastic polypropylene carbonate.
6. System according to claim 5, characterized in that said third oxidation unit (11) comprises: the propylene oxidation device (111) is used for carrying out third oxidation reaction on propylene to obtain a mixed product;
the pre-separation device (112) is communicated with the propylene oxidation device (111) and is used for pre-separating the mixed product to obtain a crude product, a mixed gas and a byproduct;
and the product purification device (113) is communicated with the pre-separation device (112) and is used for purifying the crude product to obtain the refined propylene oxide.
7. The system according to claim 6, wherein the third oxidation unit (11) further comprises: the propylene purification device (114) is communicated with the top end of the pre-separation device (112) and is used for separating the mixed gas to obtain propylene and propane;
the top end of the propylene purification device (114) is communicated with the propylene oxidation device (111) and is used for circularly introducing the separated propylene into the propylene oxidation device (111).
8. The system of claim 5, wherein the carbon dioxide delivery unit (12) comprises: the compressors (121) are sequentially communicated and are used for boosting and compressing carbon dioxide byproducts generated in the coal-to-liquid production process to obtain compressed carbon dioxide;
a purification device (122) for purifying the compressed carbon dioxide to obtain purified carbon dioxide;
a rectification device (123) for rectifying the purified carbon dioxide to obtain high-purity carbon dioxide; and
and the cryogenic device (124) is used for freezing the high-purity carbon dioxide to obtain liquid carbon dioxide.
9. The system according to any one of claims 1 to 4, characterized in that said first polymerization unit (9) comprises: a first esterification device (91) which is communicated with the first reaction unit (2), and the first esterification device (91) is communicated with the first oxidation unit (4) and/or the second reaction unit (8) and is used for mixing 1, 4-butanediol and adipic acid to carry out a first esterification reaction to obtain a polymer A;
a second esterification device (92) which is respectively communicated with the first reaction unit (2) and the second oxidation unit (7) and is used for mixing 1,4 butanediol and terephthalic acid to carry out a second esterification reaction to obtain a polymer B; and
and the first condensation device (93) is respectively communicated with the first esterification device (91) and the second esterification device (92) and is used for mixing the polymer A and the polymer B to carry out polycondensation reaction to obtain the degradable plastic A.
10. The system according to any one of claims 1 to 4, wherein said first polymerization unit (9) comprises a third esterification device (94), in communication with said first reaction unit (2) and said second oxidation unit (7), respectively, for mixing 1, 4-butanediol and terephthalic acid for a third esterification reaction, obtaining polymer C;
a fourth esterification device (95) which is respectively communicated with the first reaction unit (2) and the third esterification device (94), is communicated with the first oxidation unit (4) and/or the second reaction unit (8), and is used for mixing 1, 4-butanediol, the polymer C and adipic acid to carry out a fourth esterification reaction to obtain a polymer D;
and the second condensation device (96) is used for carrying out polycondensation reaction on the polymer D to obtain the degradable plastic A.
11. The system according to any one of claims 1 to 4, wherein the first polymerization unit (9) comprises a fifth esterification device (97) in communication with the first reaction unit (2), the second oxidation unit (7), and the first oxidation unit (4) and/or the second reaction unit (8), respectively, for mixing 1, 4-butanediol, terephthalic acid, and adipic acid for a fifth esterification reaction to obtain polymer E;
and the third condensation device (98) is used for carrying out polycondensation reaction on the polymer E to obtain the degradable plastic A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202121463264.2U CN215480673U (en) | 2021-06-29 | 2021-06-29 | System for preparing degradable plastics by directly liquefying coal to obtain oil product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202121463264.2U CN215480673U (en) | 2021-06-29 | 2021-06-29 | System for preparing degradable plastics by directly liquefying coal to obtain oil product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN215480673U true CN215480673U (en) | 2022-01-11 |
Family
ID=79723307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202121463264.2U Active CN215480673U (en) | 2021-06-29 | 2021-06-29 | System for preparing degradable plastics by directly liquefying coal to obtain oil product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN215480673U (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386071A (en) * | 2022-04-09 | 2022-11-25 | 上海尼拜环保科技发展有限公司 | Green production process and device for degradable plastic |
| CN115403756A (en) * | 2022-08-10 | 2022-11-29 | 内蒙古君正化工有限责任公司 | Green low-carbon preparation process for efficiently preparing degradable plastics by coal |
-
2021
- 2021-06-29 CN CN202121463264.2U patent/CN215480673U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386071A (en) * | 2022-04-09 | 2022-11-25 | 上海尼拜环保科技发展有限公司 | Green production process and device for degradable plastic |
| CN115403756A (en) * | 2022-08-10 | 2022-11-29 | 内蒙古君正化工有限责任公司 | Green low-carbon preparation process for efficiently preparing degradable plastics by coal |
| CN115403756B (en) * | 2022-08-10 | 2024-04-23 | 内蒙古君正化工有限责任公司 | Green low-carbon preparation process for efficiently preparing degradable plastic from coal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN215480673U (en) | System for preparing degradable plastics by directly liquefying coal to obtain oil product | |
| US8377151B2 (en) | Process for producing a renewable biofuel from waste water treatment plants | |
| Duque‐Ingunza et al. | Process optimization for catalytic glycolysis of post‐consumer PET wastes | |
| CN102725257A (en) | Continuous process of oxidative cleavage of vegetable oils | |
| CN101845323B (en) | Process for producing petrol and diesel oil by plastic oil | |
| CN103044197A (en) | Technological method for purifying1,4-butanediol and co-producing gamma-butyrolactone | |
| CN105272941A (en) | Propylene oxide production method | |
| CN102126926A (en) | Method for recycling ethylene glycol and acetaldehyde from polyester waste water | |
| CN112851502B (en) | Method for catalyzing waste PET polyester to carry out methanol alcoholysis by using choline and terephthalic acid non-metallic ionic liquid | |
| CN104292066A (en) | Preparation method for high purity isobutylene | |
| CN113105316A (en) | Method for extracting acetophenone and styrene from phenol tar waste liquid | |
| CN103012090A (en) | Method for recovering organic matters in polyester wastewater | |
| Hu et al. | Recycling and upgrading utilization of polymer plastics | |
| US11566267B2 (en) | Method for producing organic substance | |
| CN101413156B (en) | Spandex yarn alcoholysis production process | |
| CN105194996B (en) | A kind of method of comprehensive utilization of yellow phosphoric tail gas | |
| CN105315238B (en) | The production equipment of expoxy propane | |
| TW202005950A (en) | Integrated systems and processes for chemical production | |
| CN111763167B (en) | Method for separating trace impurities by CHPPO device | |
| CN109134258A (en) | A kind of product separating technology of prepared by dimethyl oxalate plus hydrogen methyl glycollate | |
| CN114315520B (en) | Method for separating and purifying high-carbon diol by low-temperature crystallization | |
| CN210974476U (en) | Device for purifying acetic acid from acetic acid-containing wastewater | |
| CN105315234A (en) | Method used for producing epoxypropane | |
| CN112723992B (en) | Process for preparing high-purity decanediol by side-line vacuum rectification | |
| CN105272939A (en) | Epoxy propane production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |