CN112500881A - Device and method for blending waste plastics in residual oil hydrogenation device - Google Patents

Device and method for blending waste plastics in residual oil hydrogenation device Download PDF

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Publication number
CN112500881A
CN112500881A CN202011290941.5A CN202011290941A CN112500881A CN 112500881 A CN112500881 A CN 112500881A CN 202011290941 A CN202011290941 A CN 202011290941A CN 112500881 A CN112500881 A CN 112500881A
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residual oil
mixed
waste
plastic
waste plastics
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何昌春
王鹏
葛奉娟
田林
赵伟婷
张娜
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Xuzhou University of Technology
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Xuzhou University of Technology
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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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00

Abstract

The invention discloses a device and a method for blending waste plastics in a residual oil hydrogenation device, belonging to the technical field of petrochemical industry and environmental protection. The invention utilizes the existing residual oil hydrogenation device of an oil refinery to mix and heat residual oil and waste plastic which is melted and heated to a molten state in the waste plastic and then carry out hydrogenation reaction to refine into petrochemical products on the basis of the original hydrogenation process, thereby realizing the comprehensive utilization of plastic resources. The invention can not only improve the environmental condition, but also save the equipment investment cost, improve the raw material conversion rate, increase the yield of light component products, reduce the hydrogen consumption, reduce the coking, prolong the service life of the catalyst, flexibly adjust the blending proportion of residual oil and waste plastics and have higher economic benefit.

Description

Device and method for blending waste plastics in residual oil hydrogenation device
Technical Field
The invention relates to a device and a method for recycling waste plastics by utilizing the existing petrochemical device, belonging to the technical field of petrochemical industry and environmental protection.
Background
At present, plastic waste pollution harms the environment and human health. Most plastics are not naturally degradable and need to be handled by artificial methods. The common methods for treating the difficultly degradable waste plastics are direct recycling, deep landfill, thermal degradation and incineration. The direct recycling is the method for treating the plastic garbage with the highest added value, but has higher requirements on the types and the classifications of the plastics; although the deep landfill method is easy to implement, the pollution to the environment can be continuously existed for a long time, the precious land resources are occupied in a large area, and the recovery value of plastics is wasted; thermal degradation is carried out by heating and dry distillation in an air-isolated manner, so that the high molecular polymer is converted into small molecular substances, and the small molecular substances can be used for producing products such as gasoline, diesel oil and the like; the incineration method directly burns the plastic and utilizes the heat energy released by the plastic to generate electricity or produce steam.
According to the disclosure in blue book for development analysis and prospect report of China oil and gas industry (2019-. The production of petroleum products by the thermal degradation of waste plastics is an effective countermeasure.
Chinese patent (CN 108102682A) proposes a method for producing gasoline and other products by a waste oil and waste plastic co-cracking catalytic device, and waste oil blending can obviously improve heat transfer and mass transfer, reduce residues and improve gasoline quality. Chinese patent (CN 109477006A) proposes a method for simultaneously carrying out dehydrochlorination, hydrocracking and selective hydrodealkylation of C9+ aromatic hydrocarbon on plastic pyrolysis oil, and is characterized in that large-scale resource utilization of chlorine-containing plastics such as polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) can be realized. Chinese patent (CN 104611030A) proposes a coking method for producing fuel oil from waste plastics, which comprises the steps of carrying out coking reaction on high aromatic components and waste plastics or plastic oil in a delayed coking tower to produce coke, coking dry gas and coking distillate oil, wherein the coking distillate oil can be processed to obtain naphtha and diesel oil, wherein the quality of the diesel oil is better. Chinese patent (CN 109355099A) proposes a method for preparing fuel oil by co-processing solid wastes (including waste plastics and waste tires) and coal tar, which can produce products such as gasoline, diesel oil, phenols and the like, and has the advantages of low hydrogen consumption, high oil yield and the like. Chinese patent (CN 109705985A) proposes a method for producing aviation kerosene by utilizing polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT), wherein the aviation kerosene is rich in cycloparaffin and aromatic hydrocarbon components, can be blended with biological aviation kerosene mainly comprising paraffin, and solves the problems of volume heat value and sealing property of the biological aviation kerosene. Chinese patent (CN 110139846A) proposes a method for converting waste plastics into high value-added propylene and cumene, which can solve the problem of producing cumene from raw materials other than petroleum and improve the economy of bisphenol a production process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a device and a method for blending waste plastics by using a residual oil hydrogenation device, which are used for blending the waste plastics by using the existing residual oil hydrogenation device of an oil refinery, so that a polymer is subjected to pyrolysis and hydrogenation reaction at high temperature and high pressure to produce a petrochemical product, thereby realizing the comprehensive utilization of plastic resources.
The invention is realized by the following technical scheme: a device for blending waste plastics in a residual oil hydrogenation device is characterized in that: on the basis of the original residual oil hydrogenation device, a pulverizer for blending waste plastics, a dryer, a waste plastic bin, a waste plastic melting tank, a static mixer and a required solid conveying device are additionally arranged at the input end of the whole system.
The waste plastic melting tank comprises an end socket, a cylinder body and a cone, wherein a waste plastic powder inlet, a pressure gauge and a gas outlet are formed in the upper portion of the end socket, a nitrogen inlet and a jacket are formed in the cylinder body, the jacket is provided with a jacket steam inlet in the upper portion and a jacket condensed water outlet in the lower portion, a stirring paddle is arranged in the cylinder body and driven by an external motor and a speed reducer, a coil type steam heating device or a coil type electric heating device is arranged in the cone, a thermometer is arranged outside the cone, and a molten plastic outlet is formed in the lower end of the cone.
A process for blending waste plastics in residual oil hydrogenating apparatus includes such steps as loading the sorted, pulverized and dried waste plastics into the waste plastics cabin by belt conveyer, continuously or intermittently feeding the raw materials to the waste plastics smelting tank, heating the waste plastics in the waste plastics smelting tank to molten and softened state, pumping the mixture to static mixer, mixing it with fresh residual oil and circulating residual oil, and adding the mixture to hydrogenating system.
The mass ratio of the blended waste plastics to the fresh residual oil is 0-0.3, the blended waste plastics only contain carbon-hydrogen polymer plastics accounting for 50-100% of the total mass of the waste plastics, the oxygen-containing polymer plastics accounting for 0-50% of the total mass of the waste plastics, and the mass of the plastics containing other heteroatoms is less than 1% of the total mass of the waste plastics.
The waste plastic melting tank is provided with a jacket and a coil type steam heating device or a coil type electric heating device, the jacket and the coil type steam heating device or the coil type electric heating device are used for heating waste plastic, a temperature and pressure monitoring point is arranged, the operating pressure is 0-20kPaG, the waste plastic is heated to 200 ℃ plus 100 ℃ at the bottom of the melting tank, steam is adopted for heating in the jacket, the water steam saturation temperature range is 250 ℃ plus 120 ℃, the steam flow or the electric heating power is controlled by a temperature controller, a paddle type, anchor type or frame type stirrer suitable for high-viscosity liquid is selected as a stirrer for improving the heat transfer efficiency, nitrogen is introduced into the waste plastic melting tank as protective gas, and the waste plastic is heated to 350 ℃ plus 150 ℃ in the melting tank.
In the blended waste plastics, the waste plastics with higher melting temperature and the waste plastics with lower melting temperature are mixed for use so as to maintain the stability of the temperature of the plastic melting tank.
The blended waste plastic contains only hydrocarbon polymers including Polyethylene (PE), polypropylene (PP), polybutylene, Polyisobutylene (PIB), Polybutadiene (PB), Polyisoprene (PI), Polystyrene (PS), butyl rubber (IIR), Styrene Butadiene Rubber (SBR) and the like; the oxygen-containing polymer in the blended waste plastic is polyethylene glycol (PEG), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyether ether ketone (PEEK), Polycarbonate (PC), polyethylene terephthalate (PET), phenolic resin (PF) and the like; the polymer containing heteroatoms other than oxyhydrogen atoms in the blended waste plastic may be a chlorine-or nitrogen-containing polymer such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), Polyacrylonitrile (PAN), melamine resin (MF), ABS resin, etc.
When the temperature of the molten plastic at the outlet of the bottom of the waste plastic molten tank is 20 ℃ lower than or not higher than the temperature of the residual oil, the molten plastic can be mixed with the residual oil before the residual oil exchanges heat with the hydrogenation reaction effluent; when the temperature of the molten plastic at the outlet of the bottom of the waste plastic molten tank is higher than the temperature of the residual oil by more than 20 ℃, the residual oil can be mixed with the residual oil after the heat exchange between the residual oil and the hydrogenation reaction effluent.
The selected hydrogenation reactor is a fixed bed, a fluidized bed, a moving bed or a suspension bed reactor, the operation temperature is 350-;
if the blended plastics contain chlorine, the tube bundle of the air cooler of the reaction effluent and the pipeline connected with the tube bundle are made of Incoloy 825, Inconel 625 or titanium materials which are resistant to ammonium chloride corrosion;
one embodiment is: the hydrogenation reactor adopts a fixed bed reactor to carry out hydrocracking on the residual oil-waste plastic mixed raw material, and the process flow is as follows: crushing solid waste plastics S2 by a crusher, drying in a dryer, drying, conveying to a waste plastics bin, intermittently feeding the waste plastics bin to a waste plastics melting tank, heating plastic particles in the waste plastics melting tank to a molten state by steam, mixing the molten plastic S3 discharged from the waste plastics melting tank with fresh residual oil S4 and circulating residual oil S21 in a static mixer, filtering out solid particles by a filter, exchanging heat with hydrogenation reaction effluent S8 at the outlet of a fixed bed reactor in a heat exchanger, mixing the residual oil plastic mixture S6 after heat exchange with mixed hydrogen S25, heating the mixed hydrogen residual oil plastic mixture S7 in a tubular furnace to 420 ℃, feeding the heated material S7 into the fixed bed reactor for hydrogenation reaction, injecting deoxygenated water S9 after heat exchange of hydrogenation reaction effluent S8 after reaction, feeding into an air cooler for condensation and cooling, after condensation and cooling, the mixture enters a cold high-pressure separator for separation, the top gas S11 of a cold high-pressure separation tank is obtained, the bottom gas S12 of the acid sewage and the bottom oil S13 of the cold high-pressure separation tank are separated, the acid sewage S12 enters a sewage stripping device for treatment, the top gas S11 of the cold high-pressure separation tank enters a cold low-pressure separation tank for decompression and re-separation, the top gas S14 of the cold low-pressure separation tank is obtained, the bottom oil S15 of the cold low-pressure separation tank is obtained at the bottom, the bottom oil S13 of the cold high-pressure separation tank and the bottom oil S15 of the cold low-pressure separation tank are mixed and then enter a fractionating tower for separation, the top gas S17 of the light component is obtained at the top, the middle distillate S18 is obtained at the side, the wide-fraction residual S19 is obtained at the bottom, the wide-fraction S19 is mostly circulated as the circulating residual S21, the external throwing residual S20 is discharged, the top gas S14 of the cold low-fraction tank enters an absorption tower for purification, the cycle hydrogen 24 is obtained, the cycle hydrogen compressor, the, mixing with residual oil plastic mixture S6, feeding into a tube furnace, and feeding into a fixed bed reactor.
Another embodiment is: the hydrogenation reactor adopts a fluidized bed reactor to carry out hydrocracking on the residual oil-waste plastic mixed raw material, and the process flow is as follows: crushing solid waste plastics S2 by a crusher, drying in a dryer, drying, conveying to a waste plastics bin, continuously feeding the waste plastics bin to a waste plastics melting tank, heating plastic particles in the waste plastics melting tank to a molten state by jacketed steam and an electric heating wire, filtering solid particles in the molten plastic S3 discharged from the waste plastics melting tank to obtain filtered molten waste plastics S26, mixing the filtered molten waste plastics S28 with filtered mixed residual oil S28 filtered by a filter and subjected to heat exchange by a heat exchanger in a static mixer, mixing the mixed residual oil plastic mixture S5 with mixed hydrogen S25, heating the mixed hydrogen residual oil plastic mixture S7 in a tubular furnace to 440 ℃, feeding the heated material S7 into a fluidized bed reactor for hydrogenation reaction, and exchanging heat between the hydrogenated reaction effluent S8 after reaction and the filtered mixed residual oil S28 in the heat exchanger, after heat exchange, the mixture enters a hot high-pressure separator for gas-liquid separation, hot high-fraction tank top gas S29 is obtained at the top, hot high-fraction tank bottom oil S30 is obtained at the bottom, the hot high-fraction tank top gas S29 is injected into deaerated water S9, the mixture enters an air cooler for condensation and cooling, the mixture enters a cold high-pressure separator for separation after the condensation and cooling are completed, cold high-fraction tank top gas S11 is obtained at the top, acid sewage S12 and cold high-fraction tank bottom oil S13 are separated at the bottom, the acid sewage S12 enters a sewage stripping device for treatment, the cold high-fraction tank bottom oil S13 enters a cold low-pressure separation tank for decompression and re-separation, cold low-fraction tank top gas S14 is obtained at the top, cold low-fraction tank bottom oil S15 is obtained at the bottom, the cold low-fraction tank top gas S14 enters a recovery device for recovering useful components, the hot high-fraction tank bottom oil S30 and the cold low-fraction tank bottom oil S15 are mixed into distillate oil S16 for separation, the light fraction oil S17 is obtained at the top of a, obtaining wide fraction residual oil S19 at the bottom of the tower, recycling most of wide fraction residual oil S19 as cycle residual oil S21, discharging a small part of the wide fraction residual oil S19 as external throwing residual oil S20, mixing cycle residual oil S21 with fresh residual oil S4 to obtain mixed residual oil S27, feeding the mixed residual oil S11 into an absorption tower for purification, obtaining cycle hydrogen S24 after purification, mixing the purified cycle hydrogen S24 with new hydrogen S1 pressurized by a new hydrogen compressor to obtain mixed hydrogen S25 after compression by a cycle hydrogen compressor, mixing the mixed hydrogen S25 with a residual oil plastic mixture S5, feeding the mixed hydrogen S5 into a tubular furnace, and feeding the mixed hydrogen into a fluidized bed reactor.
The invention has the beneficial effects that:
(1) the main equipment of the invention utilizes residual oil hydrogenation equipment of the existing oil refinery, does not need to additionally invest in a waste plastic pyrolysis device, has less equipment investment and only needs some pretreatment and mixing devices;
(2) the hydrogen consumption of the raw material in unit volume is lower than that of the original process, the residual oil circulation ratio and the external residual oil throwing amount are reduced, the yield of light fractions and middle fractions such as residual oil hydrogenated fraction oil is improved, and the economic benefit can be improved;
(3) the invention can improve the carbon-hydrogen ratio of the hydrogenation raw material, reduce the metal content and the sulfur-nitrogen content of the hydrogenation raw material, reduce coking and prolong the service life of the catalyst.
(4) The invention can flexibly adjust the blending proportion of the waste plastics according to the supply condition of the waste plastics and the market quotation of the raw material products at any time.
Drawings
The invention is further illustrated below with reference to the figures and examples.
FIG. 1 is a schematic process flow diagram of the process of the present invention;
FIG. 2 is a schematic process flow diagram of another process of the present invention;
FIG. 3 is a schematic view showing a structure of a waste plastic melting tank;
FIG. 4 is another schematic view of the structure of a waste plastic melting tank.
In the figure, 1-fresh hydrogen compressor, 2-pulverizer, 3-dryer, 4-waste plastic silo, 5-waste plastic melting tank, 6-static mixer, 7-filter, 8-heat exchanger, 9-tube furnace, 10-fixed bed reactor, 11-reaction effluent air cooler, 12-cold high pressure separator, 13-cold low pressure separator, 14-fractionating tower, 15-absorption tower, 16-recycle hydrogen compressor; 17-molten waste plastic filter, 18-fluidized bed reactor, 19-hot high pressure separator.
In the structure of the waste plastic melting tank, 51-end enclosure, 52-cylinder, 53-cone, 501-waste plastic powder inlet, 502-nitrogen inlet, 503-jacket steam inlet, 504-jacket, 505-coil steam inlet, 506-thermometer, 507-molten plastic outlet, 508-coil condensed water outlet, 509-steam coil, 510-jacket condensed water outlet, 511-stirring paddle, 512-pressure gauge, 513-gas outlet, 514-speed reducer, 515-motor and 516-electric heating coil.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
Techniques, methods, and apparatus known to those skilled in the art may not be discussed in detail but are intended to be part of the specification as appropriate.
The device for blending waste plastics of a residual oil hydrogenation device shown in figures 1-4 is additionally provided with a pulverizer 2 for blending waste plastics, a dryer 3, a waste plastic bin 4, a waste plastic melting tank 5, a static mixer 6 and a required solid conveying device at the input end of the whole system on the basis of the original residual oil hydrogenation device.
The waste plastic melting tank 5 comprises an end enclosure 51, a cylinder 52 and a cone 53, wherein the upper part of the end enclosure 51 is provided with a waste plastic powder inlet 501, a pressure gauge 512 and a gas outlet 513, the cylinder 52 is provided with a nitrogen inlet 502 and a jacket 504, the jacket 504 is provided with a jacket steam inlet 503 at the upper part and a jacket condensed water outlet 510 at the lower part, a stirring paddle 511 is arranged in the cylinder 52, the stirring paddle 511 is driven by an external motor 515 and a speed reducer 514, a coil type steam heating device or a coil type electric heating device is arranged in the cone 53, the cone 53 is externally provided with a thermometer 506, and the lower end of the cone 53 is provided with a molten plastic outlet 507.
The method for blending waste plastics by a residual oil hydrogenation device as shown in fig. 1-4 comprises the steps of conveying sorted, crushed and dried waste plastics into a waste plastic bin 4 by a belt conveyer, continuously or intermittently feeding materials into a waste plastic melting tank 5 from the waste plastic bin 4, heating the waste plastics in the waste plastic melting tank 5 to a molten and softened state, pumping the materials to a static mixer 6 to be uniformly mixed with fresh residual oil and circulating residual oil, mixing the mixed materials with mixed hydrogen, and feeding the mixed materials as a hydrogenation raw material into a hydrogenation system. The static mixer is suitable for mixing high-viscosity fluid, such as SK type and SX type static mixers.
The mass ratio of the blended waste plastics to the fresh residual oil is 0-0.3, the blended waste plastics only contain carbon-hydrogen polymer plastics accounting for 50-100% of the total mass of the waste plastics, the oxygen-containing polymer plastics accounting for 0-50% of the total mass of the waste plastics, and the mass of the plastics containing other heteroatoms is less than 1% of the total mass of the waste plastics.
The waste plastic melting tank 5 is provided with a jacket 504 and a coil type steam heating device or a coil type electric heating device, the jacket and the coil type steam heating device or the coil type electric heating device are used for heating waste plastic, a temperature and pressure monitoring point is arranged, the operating pressure is 0-20kPaG, the waste plastic is heated to 200 ℃ plus 100 ℃ at the bottom of the melting tank, steam is adopted for heating in the jacket, the water steam saturation temperature range is 250 ℃ plus 120 ℃, the steam flow or the electric heating power is controlled by a temperature controller, a paddle type, anchor type or frame type stirrer suitable for high-viscosity liquid is selected as a stirrer for improving the heat transfer efficiency, nitrogen is introduced into the waste plastic melting tank 5 as protective gas, and the waste plastic is heated to 350 ℃ plus 150 ℃ in the waste plastic melting tank 5.
In the blended waste plastics, the waste plastics with higher melting temperature and the waste plastics with lower melting temperature are mixed for use so as to maintain the stability of the temperature of the plastic melting tank.
The blending waste plastics are mainly polymers only containing carbon and hydrogen, such as Polyethylene (PE), polypropylene (PP), polybutylene, Polyisobutylene (PIB), Polybutadiene (PB), Polyisoprene (PI), Polystyrene (PS), butyl rubber (IIR), Styrene Butadiene Rubber (SBR) and the like; partially oxygen-containing polymers such as polyethylene glycol (PEG), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyether ether ketone (PEEK), Polycarbonate (PC), polyethylene terephthalate (PET), phenol resin (PF), etc. may be blended; in addition, a small amount of a chlorine-containing polymer such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and a nitrogen-containing polymer such as Polyacrylonitrile (PAN), melamine resin (MF), ABS resin, and the like, which have a hetero atom other than carbon, hydrogen, and oxygen, may be blended.
When the temperature of the molten plastic at the outlet of the bottom of the waste plastic molten tank is 20 ℃ lower than or not higher than the temperature of the residual oil, the molten plastic can be mixed with the residual oil before the residual oil exchanges heat with the hydrogenation reaction effluent; when the temperature of the molten plastic at the outlet of the bottom of the waste plastic molten tank is higher than the temperature of the residual oil by more than 20 ℃, the residual oil can be mixed with the residual oil after the heat exchange between the residual oil and the hydrogenation reaction effluent.
The hydrogenation reactor is a fixed bed, a fluidized bed, a moving bed or a suspension bed reactor, the operation temperature is 350-500 ℃, the operation pressure is 5-25 MPa, and the catalyst is selected from FZC series developed by the petrochemical research institute, MicroCat of Honeywell UOP company, RF-1000 of AKIO company or TK719, TK751 and TK773 residual oil hydrogenation catalysts of TK7XX series of Criterion company.
If the blended plastics contain chlorine, the pipe bundle of the reaction effluent air cooler REAC and the pipeline connected with the pipe bundle are made of materials such as Incoloy 825, Inconel 625 or titanium materials which are resistant to ammonium chloride corrosion or materials similar to the materials.
Example 1:
in this example, a fixed bed reactor was used to conduct hydrocracking of a residue-waste plastic mixed feedstock, the waste plastic was a mixture of Polyethylene (PE) and polypropylene (PP), the residue was atmospheric residue, the waste plastic accounted for 20% of the feedstock specific gravity, the mass percentages of PE and PP in the waste plastic were 60% and 40%, respectively, and the main process parameters are shown in table 1.
The process flow diagram is shown in figure 1, and the material flows in figure 1 are as follows: s1-new hydrogen, S2-solid waste plastic, S3-molten waste plastic, S4-fresh residual oil, S5-residual oil plastic mixture, S6-filtered residual oil plastic mixture, S7-mixed hydrogen residual oil plastic mixture, S8-hydrogenation reaction effluent, S9-deoxygenated water, S10-water injection reaction effluent, S11-cold high-split tank top gas, S12-acid sewage, S13-cold high-split tank bottom oil, S14-cold low-split tank top gas, S15-cold low-split tank bottom oil, S16-mixed tank bottom oil, S17-fuel gas and wide-cut gasoline, S18-middle distillate, S19-wide-cut residual oil, S20-external-thrown residual oil, S21-circulating residual oil, S22-absorbent lean liquid, S23-absorbent rich liquid, S24-circulating hydrogen and S25-mixed hydrogen.
The process flow is as follows: the solid waste plastics S2 is crushed by a crusher 2, enters a dryer 3 for drying, is conveyed into a waste plastics bin 4 after being dried, the waste plastics bin 4 feeds materials into a waste plastics melting tank 5 intermittently, plastic particles are heated to a molten state by water vapor in the waste plastics melting tank 5 (see figure 3), the molten plastics S3 discharged from the waste plastics melting tank 5 are mixed with fresh residual oil S4 and circulating residual oil S21 in a static mixer 6, solid particles are filtered out by a filter 7, the solid particles and hydrogenation reaction effluent S8 at the outlet of a fixed bed reactor 10 exchange heat in a heat exchanger 8, the residual oil plastic mixture S6 after heat exchange is mixed with mixed hydrogen S25, the mixed hydrogen-mixed residual oil plastic mixture S7 enters a tubular furnace 9 for heating to 420 ℃, the heated material S7 enters the fixed bed reactor 10 for hydrogenation reaction, the hydrogenation reaction effluent S8 after reaction is subjected to heat exchange and then is injected with water S9 for deoxidization, the mixture enters an air cooler 11 for condensation cooling, the mixture enters a cold high-pressure separator 12 for separation after the condensation cooling is finished, cold high-pressure separation tank top gas S11 is obtained at the top, acid sewage S12 and cold high-pressure separation tank bottom oil S13 are separated at the bottom, the acid sewage S12 enters a sewage stripping device for treatment, the cold high-pressure separation tank top gas S11 enters a cold low-pressure separation tank 13 for decompression and re-separation, cold low-pressure separation tank top gas S14 is obtained at the top, cold low-pressure separation tank bottom oil S15 is obtained at the bottom, the cold high-pressure separation tank bottom oil S13 and the cold low-pressure separation tank bottom oil S15 are mixed and then enter a fractionating tower 14 for separation, light component fuel gas and gasoline S17 are obtained at the top, middle distillate S18 is obtained at the bottom, wide fraction residual oil S19 is obtained at the bottom, most of the wide fraction residual oil S19 is used as circulating residual oil S21 for circulation, a small part of the side line is used as an external throwing S20 discharge device, the cold low-fraction tank top, after being compressed by the recycle hydrogen compressor 16, the mixed hydrogen is mixed with the pressurized fresh hydrogen S1 of the fresh hydrogen compressor 1 to form mixed hydrogen S25, and the mixed hydrogen is mixed with the residual oil plastic mixture S6 and then enters the tubular furnace 9 and then enters the fixed bed reactor 10.
The total conversion rate of the original residue oil hydrogenation process is 88.63 percent, the yield of fuel gas and gasoline is 30.03 percent, and the hydrogen consumption is 102.4m3H2/m3The total conversion rate of the raw materials mixed with plastics is 91.10%, the yield of fuel gas and gasoline is 32.85%, and the hydrogen consumption is 95.2Nm3H2/m3The raw materials can obviously improve the conversion rate of the raw materials, increase the yield of light components and reduce the hydrogen consumption.
Table 1 main process parameters of example 1
Process parameters Numerical value Process parameters Numerical value
Residual oil throughput (ten thousand tons/year) 50 Total conversion of starting materials (%) 91.10
Waste plastic treatment capacity (ten thousand tons per year) 10 Fuel gas and gasoline yield (ten thousand tons per year) 19.71
Reaction operating pressure (MPa) 15 Middle distillate yield (ten thousand tons/year) 34.95
Reaction temperature (. degree.C.) 380-420 Fuel gas and gasoline yield (%) 32.85
Catalyst and process for preparing same FZC-36 Middle distillate yield (%) 58.25
Temperature of bottom of molten pool of waste Plastic (. degree. C.) 180 External slag oil throwing amount (ten thousand tons/year) 5.22
Operating pressure of waste plastic melting tank (kPaG) 10-15 Emptying and other loss (ten thousand tons/year) 0.12
Waste plastic melting tank steam consumption (t/h) 2.9 Hydrogen consumption (Nm)3H2/m3Raw materials) 95.2
Example 2:
in the example, a fluidized bed reactor is used for hydrocracking of a residue-waste plastic mixed raw material, the waste plastic is a mixture of Polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA) and polyvinyl chloride (PVC), the residue is vacuum residue, the waste plastic accounts for 13.0 percent of the raw material, the mass percentages of the PE, PP, PVA, PMMA and PVC in the waste plastic are respectively 30.5 percent, 26.3 percent, 19.2 percent, 23.1 percent and 0.9 percent, and the main process parameters are shown in Table 2.
FIG. 2 is a schematic process flow diagram of another process of the present invention.
The logistics are as follows: s1-new hydrogen, S2-solid waste plastic, S3-molten waste plastic, S4-fresh residual oil, S5-residual oil plastic mixture, S7-hydrogen-mixed residual oil plastic mixture, S8-hydrogenation reaction effluent, S9-deoxygenated water, S10-water injection reaction effluent, S11-cold high-pressure-separation tank top gas, S12-acid sewage, S13-cold high-pressure-separation tank bottom oil, S14-cold low-pressure-separation tank top gas, S15-cold low-pressure-separation tank bottom oil, S16-mixed tank bottom oil, S17-fuel gas and wide-cut gasoline, S18-middle distillate, S19-wide-cut residual oil, S20 external throwing residual oil, S21-circulating residual oil, S22-absorbent lean liquid, S23-absorbent rich liquid, S24-circulating hydrogen, S25-mixed hydrogen, S26-filtered molten residual oil, S27-mixed residual oil, s28-filtering and mixing residual oil, S29-hot high-molecular tank top gas and S30-hot high-molecular tank bottom oil.
The process flow diagram is shown in figure 2, and the process flow is as follows: the solid waste plastics S2 is crushed by a crusher 2, enters a dryer 3 for drying, is conveyed into a waste plastics bin 4 after being dried, the waste plastics bin 4 continuously feeds materials into a waste plastics melting tank 5, plastic particles are heated to a molten state in the waste plastics melting tank 5 by steam and an electric heating wire of a jacket, the molten plastics S3 discharged from the waste plastics melting tank 5 enters a molten waste plastics filter 17 to filter solid particles to obtain filtered molten waste plastics S26, is mixed with filtered mixed residual oil S28 after being filtered by a filter 7 and exchanging heat with a heat exchanger 8 in a static mixer 6, the mixed residual oil plastic mixture S5 is mixed with mixed hydrogen S25, the mixed hydrogen mixed residual oil plastic mixture S7 enters a tubular furnace 9 to be heated to 440 ℃, the heated material S7 enters a fluidized bed reactor 18 for hydrogenation reaction, the hydrogenation reaction effluent S8 after the reaction exchanges heat with the filtered mixed residual oil S28 in the heat exchanger 8, after heat exchange, the mixture enters a hot high-pressure separator 19 for gas-liquid separation, hot high-pressure separation tank top gas S29 is obtained at the top, hot high-pressure separation tank bottom oil S30 is obtained at the bottom, hot high-pressure separation tank top gas S29 is injected into deaerated water S9, the mixture enters an air cooler 11 for condensation and cooling, after the condensation and cooling are completed, the mixture enters a cold high-pressure separator 12 for separation, cold high-pressure separation tank top gas S11 is obtained at the top, acidic sewage S12 and cold high-pressure separation tank bottom oil S13 are separated at the bottom, acidic sewage S12 enters a sewage stripping device for treatment, cold high-pressure separation tank bottom oil S13 enters a cold low-pressure separation tank 13 for pressure reduction and re-separation, cold low-fraction tank top gas S14 is obtained at the top, cold low-fraction tank bottom oil S15 is obtained at the bottom, cold low-fraction tank top gas S14 enters a recovery device for recovering useful components, hot high-fraction tank bottom oil S30 and cold low-fraction tank bottom oil S15 are mixed into mixed tank bottom oil S16 for separation, and light fraction, middle distillate S18 is obtained at the side line, wide fraction residual S19 is obtained at the bottom of the tower, most of the wide fraction residual S19 is used as circulating residual S21 to be circulated, a small part of the wide fraction residual S19 is used as an external throwing residual S20 discharging device, the circulating residual S21 is mixed with fresh residual S4 to form mixed residual S27 which enters a filter 7, cold high-pressure separation tank overhead S11 enters an absorption tower 15 to be purified to form circulating hydrogen S24, the circulating hydrogen S24 is compressed by a circulating hydrogen compressor 16 and then is mixed with new hydrogen S1 pressurized by a new hydrogen compressor 1 to form mixed hydrogen S25, and the mixed hydrogen S25 is mixed with a residual plastic mixture S5 and then enters a tubular furnace 9 and then enters a.
The total conversion rate of the crude residue oil hydrogenation process is 73.4 percent, the yield of fuel gas and gasoline is 27.94 percent, and the hydrogen consumption is 140.8Nm3H2/m3The total conversion rate of the raw materials and the mixed raw materials after blending plastics is 77.62 percent, the yield of the fuel gas and the gasoline is 29.67 percent, and the hydrogen consumption is 129.7Nm3H2/m3The raw materials can obviously improve the conversion rate of the raw materials, increase the yield of light components and reduce the hydrogen consumption.
Both the air cooler 13 and the cold high-pressure separator 14 in this embodiment are made of Incoloy 825 material.
Table 2 main process parameters of example 2
Process parameters Numerical value Process parameters Numerical value
Residual oil throughput (ten thousand tons/year) 80 Total conversion of starting materials (%) 77.62
Waste plastic treatment capacity (ten thousand tons per year) 12 Fuel gas and gasoline yield (ten thousand tons per year) 27.30
Reaction operating pressure (MPa) 18 Middle distillate yield (ten thousand tons/year) 44.11
Reaction temperature (. degree.C.) 420 Fuel gas and gasoline yield (%) 29.67
Catalyst and process for preparing same FZC-40 Middle distillate yield (%) 47.95
Temperature of bottom of plastic melting tank (. degree. C.) 300 External slag oil throwing amount (ten thousand tons/year) 20.38
Operating pressure of plastic melting tank (kPaG) 10-18 Emptying and other loss (ten thousand tons/year) 0.21
Steam consumption of plastic melting tank (t/h) 1.5 Hydrogen consumption (Nm)3H2/m3Raw materials) 129.7
Power consumption of plastic melting tank (MW) 1.2
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A device for blending waste plastics in a residual oil hydrogenation device is characterized in that:
on the basis of the original residual oil hydrogenation device, a pulverizer (2) for blending waste plastics, a dryer (3), a waste plastic bin (4), a waste plastic melting tank (5), a static mixer (6) and a required solid conveying device are additionally arranged at the input end of the whole system.
2. The apparatus for converting waste plastics into residue hydrogenation apparatus according to claim 1, wherein:
the waste plastic melting tank (5) comprises a sealing head (51), a cylinder body (52) and a cone (53), a waste plastic powder inlet (501), a pressure gauge (512) and a gas outlet (513) are arranged at the upper part of the sealing head (51), a nitrogen inlet (502) and a jacket (504) are arranged on the cylinder body (52), the jacket (504) is provided with a jacket steam inlet (503) at the upper part and a jacket condensed water outlet (510) at the lower part, a stirring paddle (511) is arranged in the cylinder body (52), the stirring paddle (511) is driven by an external motor (515) and a speed reducer (514), a coil type steam heating device or a coil type electric heating device is arranged in the cone (53), a thermometer (506) is arranged outside the cone (53), and a molten plastic outlet (507) is arranged at the lower end of the cone (53).
3. A method for blending waste plastics in a residual oil hydrogenation device is characterized by comprising the following steps:
the waste plastics after being sorted, crushed and dried are conveyed into a waste plastic bin (4) through a belt conveyer, the waste plastic bin (4) continuously or intermittently feeds materials into a waste plastic melting tank (5), the waste plastics are heated to a melting and softening state in the waste plastic melting tank (5), and then the waste plastics are pumped into a static mixer (6) to be uniformly mixed with fresh residual oil and circulating residual oil, and the mixed materials are mixed with mixed hydrogen and then enter a hydrogenation system as a raw material for hydrogenation reaction.
4. A process for upgrading waste plastics for a residuum hydrotreater according to claim 3, characterized in that:
the mass ratio of the blended waste plastics to the fresh residual oil is 0-0.3, the blended waste plastics only contain carbon-hydrogen polymer plastics accounting for 50-100% of the total mass of the waste plastics, the oxygen-containing polymer plastics accounting for 0-50% of the total mass of the waste plastics, and the mass of the plastics containing other heteroatoms is less than 1% of the total mass of the waste plastics.
5. A process for upgrading waste plastics for a residuum hydrotreater according to claim 3, characterized in that:
the waste plastic melting tank (5) is provided with a jacket (504), a coil type steam heating device (509) or a coil type electric heating device (516), the jacket and the coil type steam heating device or the coil type electric heating device are used for heating waste plastic, a temperature and pressure monitoring point is arranged, the operating pressure is 0-20kPaG, the waste plastic is heated to 100-.
6. The method for blending waste plastics in a residual oil hydrogenation plant according to claim 3 or 4, characterized in that:
in the blended waste plastics, the waste plastics with higher melting temperature and the waste plastics with lower melting temperature are mixed for use so as to maintain the stability of the temperature of the plastic melting tank; the blended waste plastic contains polymers only containing hydrocarbon, such as Polyethylene (PE), polypropylene (PP), polybutylene, Polyisobutylene (PIB), Polybutadiene (PB), Polyisoprene (PI), Polystyrene (PS), butyl rubber (IIR), Styrene Butadiene Rubber (SBR) and the like; the oxygen-containing polymer in the blended waste plastic comprises polyethylene glycol (PEG), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyether ether ketone (PEEK), Polycarbonate (PC), polyethylene terephthalate (PET), phenolic resin (PF) and the like; the blended waste plastics containing polymers having heteroatoms other than carbon, hydrogen and oxygen include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), Polyacrylonitrile (PAN), melamine resin (MF), ABS resin, etc.
7. A process for upgrading waste plastics for a residuum hydrotreater according to claim 3, characterized in that:
when the temperature of the molten plastic at the outlet of the bottom of the waste plastic molten tank is 20 ℃ lower than or not higher than the temperature of the residual oil, the molten plastic can be mixed with the residual oil before the residual oil exchanges heat with the hydrogenation reaction effluent; when the temperature of the molten plastic at the outlet of the bottom of the waste plastic molten tank is higher than the temperature of the residual oil by more than 20 ℃, the residual oil can be mixed with the residual oil after the heat exchange between the residual oil and the hydrogenation reaction effluent.
8. A process for upgrading waste plastics for a residuum hydrotreater according to claim 3, characterized in that:
the selected hydrogenation reactor is a fixed bed, a fluidized bed, a moving bed or a suspension bed reactor, the operation temperature is 350-;
if the blended plastics contain chlorine, the material of the tube bundle of the Reaction Effluent Air Cooler (REAC) and the pipe connected with the tube bundle is selected from Incoloy 825, Inconel 625 or titanium material and the like which are resistant to ammonium chloride corrosion.
9. A process for upgrading waste plastics for a residuum hydrotreater according to claim 3, characterized in that:
the hydrogenation reactor adopts a fixed bed reactor (10) to carry out hydrocracking on the residual oil-waste plastic mixed raw material, and the process flow is as follows: the solid waste plastic S2 is crushed by a crusher (2), enters a dryer (3) for drying, is conveyed into a waste plastic bin (4) after being dried, the waste plastic bin (4) feeds materials into a waste plastic melting tank (5) intermittently, plastic particles are heated to a molten state in the waste plastic melting tank (5) by water vapor, the molten plastic S3 discharged from the waste plastic melting tank (5) is mixed with fresh residual oil S4 and circulating residual oil S21 in a static mixer (6), solid particles are filtered out by a filter (7), and exchanges heat with hydrogenation reaction effluent S8 at the outlet of a fixed bed reactor (10) in a heat exchanger (8), the residual oil plastic mixture S6 after heat exchange is mixed with mixed hydrogen S25, the mixed hydrogen residual oil plastic mixture S7 enters a tubular furnace (9) for heating to 420 ℃, and the heated material S7 enters a fixed bed reactor (10) for hydrogenation reaction, after heat exchange, the hydrogenation reaction effluent S8 after reaction is injected with deoxygenated water S9, enters an air cooler (11) for condensation and cooling, enters a cold high-pressure separator (12) for separation after condensation and cooling are completed, cold high-pressure separation tank top gas S11 is obtained at the top, acid sewage S12 and cold high-pressure separation tank bottom oil S13 are separated at the bottom, acid sewage S12 enters a sewage stripping device for treatment, cold high-pressure separation tank top gas S11 enters a cold low-pressure separation tank (13) for decompression and re-separation, cold low-pressure separation tank top gas S14 is obtained at the top, cold low-pressure separation tank bottom oil S15 is obtained at the bottom, cold high-pressure separation tank bottom oil S13 and cold low-pressure separation tank bottom oil S15 are mixed and then enter a fractionating tower (14) for separation, light component fuel gas and gasoline S17 are obtained at the top of the tower, middle distillate S18 is obtained at the side, wide-fraction residual S19 is obtained, most of the wide-fraction S19 is recycled as recycle S21, and a small part of residual S20 is, the cold low-molecular tank top gas S14 enters an absorption tower (15) for purification, namely recycle hydrogen S24 after purification, is compressed by a recycle hydrogen compressor (16), is mixed with new hydrogen S1 pressurized by a new hydrogen compressor (1) to form mixed hydrogen S25, is mixed with a residual oil plastic mixture S6, enters a tubular furnace (9), and then enters a fixed bed reactor (10).
10. A process for upgrading waste plastics for a residuum hydrotreater according to claim 3, characterized in that:
the hydrogenation reactor adopts a fluidized bed reactor (18) to carry out hydrocracking on the residual oil-waste plastic mixed raw material, and the process flow is as follows: the solid waste plastics S2 is crushed by a crusher (2), then enters a dryer (3) for drying, then is conveyed into a waste plastics bin (4), the waste plastics bin (4) continuously feeds materials into a waste plastics melting tank (5), plastic particles are heated to a molten state in the waste plastics melting tank (5) by jacketed water vapor and an electric heating wire, the molten plastics S3 discharged from the waste plastics melting tank (5) enter a molten waste plastics filter (17) for filtering solid particles to obtain filtered molten waste plastics S26, the filtered molten waste plastics S28 is mixed with filtered mixed residual oil S28 which is filtered by a filter (7) and heat exchanged by a heat exchanger (8) in a static mixer (6), the mixed residual oil plastic mixture S5 is mixed with mixed hydrogen S25, the mixed hydrogen mixed residual oil plastic mixture S7 enters a tubular furnace (9) for heating to 440 ℃, the heated material S7 enters a fluidized bed reactor (18) for hydrogenation reaction, the hydrogenation reaction effluent S8 after the reaction and the filtered mixed residual oil S28 exchange heat in a heat exchanger (8), the heat exchange is carried out, the hot high-pressure separation tank top gas S29 is obtained at the top, the heat exchange tank bottom oil S30 is obtained at the bottom, the hot high-pressure separation tank top gas S29 is injected into deoxygenated water S9, the cold high-pressure separation tank top gas S11 is obtained at the top, the acid sewage S12 and the cold high-pressure separation tank bottom oil S13 are separated at the bottom, the acid sewage S12 enters a sewage stripping device for treatment, the cold high-pressure separation tank bottom oil S13 enters a cold low-pressure separation tank (13) for decompression and re-separation, the cold low-pressure separation tank top gas S14 is obtained at the top, the cold low-separation tank bottom oil S15 is obtained at the bottom oil S14, the cold low-separation tank top, the cold-low-, separating the top of the tower to obtain light component fuel gas and gasoline S17, obtaining middle distillate oil S18 at the side line, obtaining wide fraction residual oil S19 at the bottom of the tower, recycling most of the wide fraction residual oil S19 as recycling residual oil S21, discharging a small part of the wide fraction residual oil S19 as external throwing residual oil S20, mixing the recycling residual oil S21 with fresh residual oil S4 to obtain mixed residual oil S27, feeding the mixed residual oil S27 into a filter (7), feeding cold high fraction tank top gas S11 into an absorption tower (15) for purification, obtaining recycling hydrogen S24 after purification, compressing the gas by a recycling hydrogen compressor (16), mixing the gas with new hydrogen S1 pressurized by a new hydrogen compressor (1) to obtain mixed hydrogen S25, mixing the gas with residual oil plastic mixture S5, feeding into a tubular furnace (9), and then feeding into.
CN202011290941.5A 2020-11-17 2020-11-17 Device and method for blending waste plastics in residual oil hydrogenation device Withdrawn CN112500881A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11939532B2 (en) 2022-01-25 2024-03-26 Braskem S.A. Methods and systems for co-feeding waste plastics into a refinery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11939532B2 (en) 2022-01-25 2024-03-26 Braskem S.A. Methods and systems for co-feeding waste plastics into a refinery

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