CN111363580A - Method and device for hydrotreating waste plastic - Google Patents
Method and device for hydrotreating waste plastic Download PDFInfo
- Publication number
- CN111363580A CN111363580A CN201811595959.9A CN201811595959A CN111363580A CN 111363580 A CN111363580 A CN 111363580A CN 201811595959 A CN201811595959 A CN 201811595959A CN 111363580 A CN111363580 A CN 111363580A
- Authority
- CN
- China
- Prior art keywords
- reactor
- oil
- liquid
- reaction
- phase hydrogenation
- 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.)
- Pending
Links
Images
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/26—Fuel gas
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for hydrotreating waste plastic, comprising the following steps: s1, adding the waste plastics into a first liquid phase hydrogenation reactor to carry out hydrocracking reaction, wherein the hydrocracking reaction conditions are as follows: obtaining a cracking product at the pressure of 1-3MPa, the temperature of 500-700 ℃ and the time of 20-90 minutes; s2, feeding the cracking product or the cracking product and an oil raw material into a second liquid phase hydrogenation reactor, and carrying out a hydroisomerization reaction, wherein the weight ratio of the cracking product to the Fischer-Tropsch wax is 1:0.5-3, and the conditions of the hydroisomerization reaction are as follows: the pressure is 10-15MPa, the temperature is 300-; the oil raw material is selected from at least one of paraffin-based distillate oil and Fischer-Tropsch wax; and S3, distilling or separating the isomeric product to obtain the lubricating oil base oil, the diesel oil and the hydrocarbon gas. The invention also relates to a device for hydrotreating waste plastic.
Description
Technical Field
The present invention relates to a method and apparatus for hydrotreating waste plastics, and more particularly to a method for treating waste plastics using a liquid-phase hydrotreating apparatus. The invention uses the liquid phase hydrogenation reactor to carry out hydrocracking and hydroisomerization reactions, and the liquid phase hydrogenation reactor adopts a multi-point quantitative hydrogen supplement mode, thereby eliminating a circulating hydrogen compressor and improving the hydrogenation efficiency.
Background
According to the latest information of the Chinese petroleum and chemical networks: the production amount of waste plastics in China all year around is about 3413 ten thousand tons, the recycling amount reaches 2487.8 more than ten thousand tons, and the waste plastics account for about 30 percent of the consumption amount of the plastics in China. The waste plastic resources are called as 'second human mineral deposit' by modern economists. The plastic raw material is a chemical product extracted from natural petroleum, the petroleum is a life pulse of modern industry and is a non-renewable natural resource, China is a net import country of petroleum, and the petroleum is related to the energy safety of the country.
The waste plastics are not easy to naturally degrade under normal conditions, and the problem of white pollution is also getting worse. With the continuous development of world economy and the continuous enhancement of environmental awareness of people, the recycling of waste plastics to produce high value-added products becomes a development trend.
Chinese patent CN104611060A discloses a method for producing clean fuel oil by using waste plastics and high aromatic components. After the high aromatic components are mixed with the waste plastic oil, the mixture firstly passes through a thermal cracking reaction zone, and the thermal cracking reaction zone adopts a mode of combining gradual temperature rise and constant temperature operation; and the obtained pyrolysis gas enters a catalytic reaction zone to contact with a catalyst in the catalytic reaction zone to perform catalytic reaction, and the obtained reaction effluent is subjected to gas-liquid separation to obtain a gas product and a liquid-phase oil product. The method can fully utilize the waste plastics and the high aromatic components, improve the yield of the light fuel oil to more than 85 percent, and obtain the diesel oil with good quality.
Chinese patent CN102703101A discloses a method for processing ethylene tar. The raw material is the mixture of ethylene tar and waste plastic or plastic oil, a one-step processing method of carrying out reaction in two reaction zones of pyrolysis and catalysis is adopted, the whole one-step processing method adopts a mode of gradually raising the temperature without a constant temperature zone, and the temperature raising rate of the thermal cracking reaction zone is high and is about 90 ℃/hr. The one-step processing method ensures that the two raw materials are quickly heated before being fully mixed; meanwhile, due to the higher heating rate, the raw materials which are just mixed can not react in time to directly generate a coke product, and the two aspects act together to result in higher residue yield and lower liquid product yield which is only about 80 wt%.
The Chinese patent CN1434100A adopts the mixed raw materials of waste plastics and oil products to prepare the fuel oil by cracking, the method solves the problem of utilization of the waste plastics, heavy oil and waste oil, but has the problems of high cracking starting temperature, low yield of light oil products such as gasoline and diesel oil fractions in liquid oil products and the like, and the heavy oil is a long-chain high-molecular-weight high-viscosity oil product generated in the petroleum production process.
Chinese patent CN101724426A discloses a method for producing high-quality diesel blending components by using waste plastic pyrolysis oil. Firstly, the density of the waste plastic pyrolysis oil at 20 ℃ is measured, and then different processing methods are selected according to the density: one is to fractionate the waste plastic pyrolysis oil with higher density and carry out hydrotreating on the heavy component obtained by fractionation to produce high-quality diesel blending component; and the other one is to hydrogenate the full fraction of the waste plastic pyrolysis oil with lower density and fractionate the hydrogenated product oil, and the obtained hydrogenated heavy component is a high-quality diesel blending component. The two processing methods provided by the invention can be realized by one set of device, the actual operation flexibility is good, and the processing flow can be flexibly switched according to the actual production requirement.
Chinese patent CN1141331A discloses a method for producing gasoline and diesel oil from waste plastics and processing gasoline fraction by hydrofining method. The method adopts a nickel hydrogenation catalyst to carry out hydrogenation treatment on the pyrolysis gasoline, and the cetane number of the diesel oil is improved by adding the cyclopentadienil into the pyrolysis diesel oil.
Chinese patent CN1114674A describes a method for preparing lubricant base oil from waste plastic cracking oil. The method polymerizes pyrolysis oil obtained by cracking waste plastics under the action of a strong acid catalyst, processes the waste plastic pyrolysis oil into lubricating oil base oil, and additionally produces a certain amount of gasoline and diesel oil. The method is complex to operate, the adopted strong acid catalyst has great pollution to the environment, and the quality of the produced gasoline and diesel oil products is not mentioned.
Chinese patent CN1331275A discloses a method for cracking petroleum products from waste plastics and a process for treating the cracked product oil. The method comprises the steps of conveying the plastic pyrolysis oil into a distillation still, adding a certain amount of antioxidant, heating, and fractionating gasoline and diesel oil respectively. The fractionated gasoline fraction is sequentially subjected to alkali washing and acid washing, and the octane number is increased and the deodorization treatment is performed by adding methyl tert-butyl ether to the treated gasoline. The fractionated diesel oil fraction is sequentially subjected to alkali washing and water washing, and a cetane number improver is added into the treated diesel oil to improve the cetane number of the product. However, the method adopts alkaline washing and acid washing means, which causes great pollution to the environment.
Chinese patent CN101932687 discloses a method for preparing lubricant base oil blending components, which comprises a cracking step, a catalytic isomerization dewaxing step and a recovery step. However, the isomerization and dewaxing step mentioned therein is to pass the cracked effluent through a fixed bed to complete the isomerization and dewaxing process under the action of hydrogenation and catalyst, and the reaction efficiency is low.
Chinese patent CN105647577 discloses a continuous liquid phase hydrogenation device, which comprises a gas-liquid mixer for mixing liquid phase material flow with hydrogen, and injecting new hydrogen into the liquid phase material flow through a hydrogen distributor to realize high-efficiency hydrogenation reaction. However, the hydrogen distribution device of the device cannot disperse hydrogen into micron-sized micro-bubbles, resulting in low reaction efficiency.
Patent US 6190542B1 discloses a method for multi-stage hydroconversion of hydrocarbon feedstock such as waste plastics, which is a process for processing a mixture of coal, residual oil and waste plastics as the main feedstock, wherein the process comprises two-stage hydrogenation, the feedstock is reacted in a first stage under the action of an iron-based catalyst, the reaction effluent is subjected to pressure reduction and separation of gas and light components, the heavy component is hydrotreated in a second stage, and the gas and light components in the second stage reaction effluent are mixed with the gas and light components in the first stage reaction effluent and then hydrotreated to produce naphtha fraction and middle distillate.
Patent US 20030199717a1 discloses a method for processing waste plastics and fischer-tropsch wax, wherein a fraction of 650-1050 ° F produced by cracking waste plastics and fischer-tropsch wax is processed by adopting a hydrotreating and isodewaxing process, and the fraction is subjected to hydrotreating and isodewaxing in sequence and then fractionated to produce diesel oil and lubricant base oil.
The waste plastic cracking oil is gasoline and diesel oil full distillate oil with a wide distillation range. Because the processing conditions of the waste plastics are different from the types of the waste plastics, the properties of the waste plastic cracking product oil are greatly different: one is high olefin content; one is high aromatic content, and both are always staggered during waste plastic production depending on the cracking feedstock.
In the field of petroleum fraction processing, high olefin content exists in coker gasoline, catalytic gasoline or coker diesel, and high aromatic content exists in catalytic gasoline and catalytic diesel. Aiming at the coking gasoline and the catalytic gasoline, the method generally adopted in petroleum refining is to remove impurities such as sulfur, nitrogen and the like, selectively remove olefin, reserve high-octane components such as aromatic hydrocarbon and the like as much as possible, select a catalyst with selective olefin reduction, and produce gasoline fractions with high-octane blending components under the process conditions of hydrogen partial pressure of 1.0-3.2 MPa and reaction temperature of 180-300 ℃. For coking diesel oil and catalytic diesel oil with high contents of olefin and aromatic hydrocarbon, hydrofining and/or hydro-upgrading technology is generally adopted, a catalyst with good hydrodesulfurization, denitrification and aromatic hydrocarbon saturation performance is adopted, and a cracking catalyst with a selective ring-opening cracking function is also adopted under certain conditions, so that the clean diesel oil blending component with low sulfur, low nitrogen and high cetane number is produced under the harsh process conditions of hydrogen partial pressure of 3.2-10.0 MPa, reaction temperature of 260-400 ℃ and the like. The method is not suitable for the full distillate oil generated by cracking the waste plastics by adopting any one of the above processing methods.
In the traditional process for preparing fuel oil from waste plastics, the waste plastics and a catalyst are put into a cracking reaction kettle together for cracking reaction, and then a cooling treatment is carried out by a cooling device to obtain products such as fuel oil. However, the process has the disadvantages of high reaction temperature, low oil yield, low added value of products and the like.
In the traditional fixed bed processing technology, a reaction device is filled with a large amount of gas, and liquid is sprayed downwards onto a catalyst bed layer. Meanwhile, in order to increase the mass transfer force, the hydrogen-oil ratio which is far greater than the reaction requirement is usually adopted, and the low flow rate of the liquid can cause the result of insufficient catalyst wetting. But in a liquid phase packed bed process. The hydrogen used in the reaction is dissolved in the liquid rather than being recycled as a gas. Therefore, the catalyst in the liquid phase hydrogenation reactor is completely wet. The presence of liquid in and around the catalyst (catalyst with good wettability) minimizes the hot spots that reduce the active sites of the catalyst. Increasing the thermal mass and achieving complete surface wetting these factors can minimize catalyst deactivation by coking.
Disclosure of Invention
In view of the problems and disadvantages of the prior art, it is an object of the present invention to provide a method for processing waste plastics using a liquid phase hydrotreater. The method adopts waste plastics as main raw materials, the waste plastics enter a hydrocracking liquid hydrogenation reactor, the hydrocracking product or paraffin-based distillate oil and Fischer-Tropsch wax are added into the hydrocracking product, and the mixture enters a hydroisomerization liquid hydrogenation reactor, and the hydroisomerization reaction process can carry out quantitative hydrogen supplement at multiple points inside and outside the reactor, and a recycle hydrogen compressor is omitted, so that the hydrogenation reaction rate is improved.
To this end, the present invention provides a method for hydroprocessing waste plastics, comprising the steps of:
s1, adding the waste plastics into a first liquid phase hydrogenation reactor to carry out hydrocracking reaction, wherein the hydrocracking reaction conditions are as follows: obtaining a cracking product at the pressure of 1-3MPa, the temperature of 500-700 ℃ and the time of 20-90 minutes;
s2, feeding the cracking product or the cracking product and an oil raw material into a second liquid phase hydrogenation reactor, and carrying out a hydroisomerization reaction, wherein the weight ratio of the cracking product to the Fischer-Tropsch wax is 1:0.5-3, and the conditions of the hydroisomerization reaction are as follows: the pressure is 10-15MPa, the temperature is 300-;
the oil raw material is selected from at least one of paraffin-based distillate oil and Fischer-Tropsch wax;
and S3, distilling or separating the isomeric product to obtain the lubricating oil base oil, the diesel oil and the hydrocarbon gas.
The method for hydrotreating waste plastic of the invention is characterized in that the temperature of the hydrocracking reaction is preferably 550-650 ℃, and the temperature of the hydroisomerization reaction is preferably 300-400 ℃.
The method for hydrotreating waste plastic of the present invention, wherein the catalyst for hydrocracking reaction is preferably prepared from a ZSM-5 molecular sieve and/or alumina.
The method for hydrotreating waste plastic of the present invention, wherein preferably, the carrier of the catalyst for hydroisomerization reaction is a carrier that is mixed in a proportion by weight of 10-20: 80-90 is prepared by mixing alumina and molecular sieve and extruding the mixture into strips, wherein the molecular sieve is at least one of ZSM-22, ZSM-23, ZSM-48 and SAPO-11.
The method for hydroprocessing waste plastics according to the present invention is characterized in that the first liquid-phase hydrogenation reactor is preferably a thermal cracking reactor, and the thermal cracking reactor is preferably one selected from the group consisting of a tank reactor, a fixed bed reactor and a fluidized bed reactor.
The method for hydrotreating waste plastic of the present invention, wherein the second liquid phase hydrogenation reactor is preferably a hydroisomerization reactor.
The method for hydrotreating waste plastic of the invention is characterized in that the VI of the lubricating oil base oil is preferably more than or equal to 120 and the pour point is preferably less than or equal to-15 ℃.
The present invention also provides an apparatus for hydrotreating waste plastic, which is an apparatus used in the above method, comprising: the hydrogen supply device is a hydrogen compressor, the hydrotreating unit consists of an oil-gas mixing device and a liquid-phase hydrogenation reactor, and the oil-gas mixing device and the liquid-phase hydrogenation reactor are respectively and independently connected with the hydrogen compressor.
The hydrogen compressor is provided with n hydrogen supply pipelines, wherein two hydrogen supply pipelines are connected with the oil-gas mixing equipment, and the rest n-2 hydrogen supply pipelines are respectively connected with the gas dispersers between the catalyst beds in the liquid phase hydrogenation reactor in a one-to-one correspondence manner.
The apparatus for hydroprocessing waste plastics according to the present invention, wherein the liquid phase hydrogenation reactor preferably comprises a first liquid phase reactor and a second liquid phase reactor.
The apparatus for hydroprocessing waste plastics according to the present invention is preferably a thermal cracking reactor, and the thermal cracking reactor is preferably one selected from a tank reactor, a fixed bed reactor and a fluidized bed reactor.
The apparatus for hydroprocessing waste plastics according to the present invention is preferably a hydroisomerization reactor.
Heating the waste plastics and mixing the waste plastics with hydrogen by an oil-gas mixing device to form a mixed raw material;
the invention has the beneficial effects that: the liquid phase hydrogenation reactor device is internally provided with n layers of catalyst bed layers and n hydrogen supplementing points, and an oil-gas mixing device is also arranged outside the reactor, so that hydrogen consumed by the reaction can be further supplemented. A product circulating pump can be cancelled, and the purposes of reducing investment and energy consumption are further achieved; meanwhile, the reaction device provided by the invention has the advantages of small volume, thin wall thickness and small tonnage, and has the effects of reducing energy consumption and reducing cost.
The device adopts a liquid phase hydrocracking reactor and a liquid phase hydroisomerization reactor which are connected in series, wherein the liquid phase hydrocracking reactor, namely a first liquid phase hydrogenation reactor, is a hydrocracking device and can remove impurities during cracking, a descending reactor (see figure 1) is adopted, and the reactor is different from a traditional trickle bed which is a liquid phase hydrogenation device and is accompanied with quantitative hydrogen supplement among beds; the liquid phase hydroisomerization reactor, i.e., the second liquid phase hydrogenation reactor, is a hydrogenation unit, the reaction that occurs is a hydroisomerization reaction, and an upward reactor (see fig. 1) is also used, and is also a liquid phase hydrogenation reaction accompanied by quantitative hydrogen supplement. The device for carrying out the hydrotreatment of the waste plastics has the following effects: the liquid phase hydrocracking reactor can better improve the cracking rate and remove impurities more thoroughly, and the liquid phase hydroisomerization reactor achieves a better hydroisomerization effect by matching with a deep hydroisomerization catalyst.
In addition, the two liquid phase hydrogenation reactors are both provided with an internal component, namely a dissolved hydrogen disperser, so that hydrogen can be better dissolved in the raw materials, the hydrogenation effect is further improved, and the reaction temperature is reduced.
In summary, the invention has the following advantages:
(1) the technical aspect is as follows: can be used for mixing the product after the waste plastic thermal cracking with Fischer-Tropsch wax or paraffin base distillate oil, and the mixed raw material enters a liquid phase hydrogenation reactor to generate high-grade lubricating oil base oil with low pour point and high viscosity index through a hydroisomerization reaction;
in the method for processing waste plastics disclosed by the invention, the isomerization dewaxing step is realized through a liquid phase hydrogenation process, and particularly, a micropore hydrogen dissolving internal member is arranged in the adopted liquid phase hydrogenation reactor, so that the effect of dispersing hydrogen into micron-sized small microbubbles and dissolving the micron-sized small microbubbles into a liquid phase raw material so as to increase the contact area between a liquid phase and a gas phase is achieved, and the reaction efficiency is greatly improved;
in the device for treating waste plastics disclosed by the invention, the liquid phase hydrogenation reactor of the hydrocracking section and the hydroisomerization dewaxing section contains a micropore hydrogen dissolving inner member (namely, the hydrogen dissolving disperser can also be called as a micropore hydrogen dissolving disperser or a hydrogen dissolving membrane tube, and is a hollow cylindrical membrane tube, the top and the periphery of the membrane tube are provided with ceramic or metal breathable membranes, the pore size of the breathable membranes is 10-90 micrometers, hydrogen enters from the bottom of the membrane tube and is diffused to the outside of the membrane tube under the action of pressure, and the hydrogen passes through the membrane tube and is dissolved in a liquid phase in a micron-level microbubble form), so that the dissolving amount of the hydrogen is greatly improved, and compared with the traditional hydrogen distribution device, the device can effectively disperse the hydrogen into micron-level small microbubbles and improve the reaction efficiency.
(2) In investment aspect: compared with the traditional hydrogenation technology, the method saves 10 to 50 percent; the high-grade lubricating oil base oil can generate higher profit value as a high value-added product.
(3) The operation cost is as follows: compared with the traditional hydrogenation technology, the method saves 25%; the load of the heating furnace is greatly reduced; the hydrogen loss amount is less; the maintenance cost of the device is lower; the catalyst dosage is lower, and the actual operation life is prolonged.
Drawings
FIG. 1 is a process flow diagram of the method of hydrotreating waste plastic of the present invention;
FIG. 2 is a schematic diagram of a hydrogen disperser;
wherein:
1. waste plastics; 2. heating furnace; 3. an oil-gas mixing device; 4. a hydrogen compressor; 5. a dissolved hydrogen disperser; 6. hydrogen gas; 7. dissolving a hydrogen product; 8. a high pressure separation tank; 9. separating the product under high pressure; 10. a desulfurization unit; 11. producing a product; 12-1, a first liquid phase hydrogenation reactor; 12-2, a second liquid phase hydrogenation reactor; 13. and (3) oil raw materials.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and specific embodiments to further understand the purpose, scheme and efficacy of the present invention, but the present invention is not limited thereto.
Referring to FIGS. 1 and 2, the apparatus for hydrotreating waste plastics of the present invention comprises: the system comprises a heating device (a heating furnace 2), a hydrotreating unit, a high-pressure separator (namely a high-pressure separation tank 8), a desulfurization device 10 and a hydrogen supply device connected with the hydrotreating unit, wherein the hydrogen supply device is a hydrogen compressor 4, the hydrotreating unit consists of an oil-gas mixing device 3 and a liquid-phase hydrogenation reactor, the oil-gas mixing device 3 and the liquid-phase hydrogenation reactor are respectively and independently connected with the hydrogen compressor 4, and the liquid-phase hydrogenation reactor comprises a first liquid-phase reactor 12-1 and a second liquid-phase reactor 12-2.
Wherein, if the waste plastic and the raw oil do not contain sulfur, the desulfurization equipment can be omitted.
Wherein the first liquid phase hydrogenation reactor 12-1 is a thermal cracking reactor, and the thermal cracking reactor is selected from one of a kettle type reactor, a fixed bed reactor and a fluidized bed reactor; the second liquid phase hydrogenation reactor 12-2 is a hydroisomerization reactor.
The hydrogen compressor 4 is provided with n hydrogen supply pipelines, wherein two hydrogen supply pipelines are connected with the oil-gas mixing device 3, the rest n-2 hydrogen supply pipelines are respectively connected with the dissolved hydrogen dispersers 5 between catalyst bed layers in the liquid phase hydrogenation reactor in a one-to-one correspondence manner, and the high-pressure separation tank 8 is connected with the desulfurization device 10 through a tail gas discharge pipeline.
Wherein, dissolve hydrogen deconcentrator 5 and also can be called as the micropore and dissolve hydrogen deconcentrator or dissolve hydrogen membrane tube, is a hollow cylinder membrane tube, and the top of membrane tube and all around are equipped with the ventilated membrane of ceramic or metal material, and the aperture size of ventilated membrane is 10-90 microns, and hydrogen gets into from the bottom of this membrane tube, diffuses to the membrane tube outside under the pressure effect, and hydrogen dissolves in the liquid phase with the form of micron order microbubble after passing through this membrane tube.
It should be noted that although fig. 1 shows two catalyst beds and one dissolved hydrogen disperser in the liquid phase hydrogenation reactor, the number n of catalyst beds in each stage may be 1, 2, 3, 4 or 5, and the dissolved hydrogen disperser 5 may be installed between catalyst beds.
The method for hydrotreating waste plastic provided by the invention comprises the following steps:
s1, adding the waste plastics into the first liquid phase hydrogenation reactor 12-1 to carry out hydrocracking reaction, wherein the hydrocracking reaction conditions are as follows: obtaining a cracking product at the pressure of 1-3MPa, the temperature of 500-700 ℃ and the time of 20-90 minutes;
s2, feeding the cracking product or the cracking product and an oil raw material into a second liquid phase hydrogenation reactor 12-2, and carrying out a hydroisomerization reaction, wherein the weight ratio of the cracking product to the Fischer-Tropsch wax is 1:0.5-3, and the hydroisomerization reaction conditions are as follows: the pressure is 10-15MPa, the temperature is 300-;
the oil raw material is selected from at least one of paraffin-based distillate oil and Fischer-Tropsch wax;
s3, distilling the isomeric product to obtain the lubricant base oil, diesel oil and hydrocarbon gas, wherein the VI of the obtained lubricant base oil is more than or equal to 120, and the pour point is less than or equal to-15 ℃.
In one embodiment, the hydrocracking catalyst is prepared from ZSM-5 molecular sieve and/or alumina; the carrier of the catalyst for the hydroisomerization reaction is 10-20 parts by weight: 80-90 is prepared by mixing alumina and molecular sieve and extruding the mixture into strips, wherein the molecular sieve is selected from at least one of ZSM-22, ZSM-23 and SAPO-11.
In the examples, the catalyst used for the hydroisomerization reaction may be Pt-ZSM23(Pt 0.3-0.55 wt%) or Pt-ZSM48(Pt 0.3-0.55 wt%).
Example 1
Referring to fig. 1 and 2, waste plastic 1(HDPE, high density polyethylene) enters an oil-gas mixing device 3 through a heating furnace 2, meanwhile, hydrogen 6 is sent to the oil-gas mixing device 3 by a hydrogen compressor 4, the waste plastic 1 and the hydrogen 6 are mixed and then enter a first liquid-phase hydrogenation reactor 12-1 for a hydrocracking reaction, the first liquid-phase hydrogenation reactor 12-1 is a thermal cracking reactor, and the thermal cracking reactor is a fixed bed reactor;
wherein, the reaction conditions of the hydrocracking reaction are as follows: the reaction temperature is 450 ℃, the hydrogen pressure is 1.5MPa, and the reaction time is 1 h. The hydrocracking reaction adopts HZSM-5 molecular sieve catalyst;
the hydrocracking reaction product and the Fischer-Tropsch wax enter an oil-gas mixing device 3 according to the mass ratio of 1:1, meanwhile, a hydrogen compressor 4 sends hydrogen 6 into the oil-gas mixing device 3, and the hydrocracking reaction product, the Fischer-Tropsch wax and the hydrogen 6 are mixed and then enter a second liquid-phase hydrogenation reactor 12-2 for hydrogenation isomerization reaction;
wherein, the reaction conditions of the hydroisomerization reaction are as follows: 350 ℃, the hydrogen pressure is 12.5MPa, and the space velocity is 0.65h-1. The catalyst adopted in the hydroisomerization reaction is Pt-ZSM23 (the mass percent of Pt is 0.3-0.55%);
and (3) feeding the hydroisomerized product, namely the dissolved hydrogen product 7, into a high-pressure separation tank 8 to obtain a product: the yield of C4 and below is 5%, the yield of naphtha fraction is 15.8%, the yield of diesel oil fraction is 27.8%, and the yield of total base oil (more than 360 ℃) of lubricating oil is 51.4%. And cutting out 2cSt base oil products at 320-400 ℃ and 8cSt base oil products at 400 ℃ from the total base oil of the lubricating oil.
And (3) according to the kinematic viscosity at 100 ℃, when the viscosity index reaches more than 120, the lubricating oil belongs to the group III lubricating oil base oil, namely high-grade lubricating oil base oil. (Category reference API lube oil Standard and Medium Petroleum lube base oil industry Standard)
The properties of the resulting product are shown in table 1.
TABLE 1 lubricating oil base oil product Properties
| 2cSt base oil products | 8cSt base oil products | |
| Kinematic viscosity at 100 DEG C | 2.6 | 7.7 |
| Kinematic viscosity at 40 ℃ | 27.8 | 43.8 |
| Viscosity index | 133 | 135 |
| Pour point | -40 | -33 |
Example 2
The difference from example 1 is that the starting material is LDPE (low density polyethylene) mixed with FT wax 1: 1. The hydrocracking and hydroisomerization reaction conditions were the same as in example 1 to obtain the product: the yield of C4 and below is 2.8%, the yield of naphtha fraction is 13.7%, the yield of diesel oil fraction is 30.5%, and the total yield of lube base oil is 55.8%. And cutting out a base oil product with 370-440 distillation range of 4CSt and a base oil product with 6cSt distillation range at more than 440 ℃ from the total base oil of the lubricating oil.
And (3) according to the kinematic viscosity at 100 ℃, when the viscosity index reaches more than 120, the lubricating oil belongs to the group III lubricating oil base oil, namely high-grade lubricating oil base oil. (Category reference API lube oil Standard and Medium Petroleum lube base oil industry Standard)
The properties of the resulting product are shown in table 2.
TABLE 2 lubricating base oil product Properties
| 4cSt base oil products | 6cSt base oil products | |
| Kinematic viscosity at 100 DEG C | 3.8 | 6.2 |
| Kinematic viscosity at 40 ℃ | 15.2 | 30.2 |
| Viscosity index | 152 | 148 |
| Pour point | -15 | -25 |
Comparative example 1
Raw material HDPE (high density polyethylene), cracking reaction conditions: normal pressure, 343 deg.C, using catalyst Ni/Mo-Al2O3(i.e., example 2 of CN 101932687A). The cracked product enters a hydroisomerization dewaxing reaction unit, and the reaction conditions are as follows: 351 ℃, 13.5MPa, 0.5LHSV, using a catalyst of Pt-SAPO11 (i.e. example 2 of CN 101932687). Obtaining a product: c4 and the following distillate yields: 10.3 percent, the yield of naphtha fraction is 8.2 percent, the yield of diesel oil fraction is 41.8 percent, and the total yield of the lubricating oil base oil is 45.3 percent.
And, from the total base oil of the lubricating oil, a 5cSt base oil product was cut. (Category reference API lube oil Standard and Medium Petroleum lube base oil industry Standard)
The properties of the resulting product are shown in table 3.
The properties of the resulting lubricant base oil product of Table 3 are as follows:
as can be seen from the data in tables 1 to 3, the obtained lubricating base oil meets the lubricating base oil standard, and the viscosity index reaches more than 120, so that the quality of the high-grade lubricating oil III-class oil is achieved. In the embodiment of the invention, under the same reaction conditions as the comparative example, the liquid yield is higher, and the lubricating oil base oil product with higher yield (the comparative gasoline and diesel oil product is a high value-added product) can be obtained. Thereby being more economical.
In summary, the invention has the following advantages:
(1) the technical aspect is as follows: can be used for mixing the product after the waste plastic thermal cracking with Fischer-Tropsch wax or paraffin base distillate oil, and the mixed raw material enters a liquid phase hydrogenation reactor to generate high-grade lubricating oil base oil with low pour point and high viscosity index through a hydroisomerization reaction;
in the method for processing waste plastics disclosed by the invention, the isomerization dewaxing step is realized through a liquid phase hydrogenation process, and particularly, a micropore hydrogen dissolving internal member is arranged in the adopted liquid phase hydrogenation reactor, so that the effect of dispersing hydrogen into micron-sized small microbubbles and dissolving the micron-sized small microbubbles into a liquid phase raw material so as to increase the contact area between a liquid phase and a gas phase is achieved, and the reaction efficiency is greatly improved;
in the device for processing waste plastics disclosed by the invention, the liquid phase hydrogenation reactors of the hydrocracking section and the hydroisomerization dewaxing section contain microporous hydrogen dissolving internals, and compared with the traditional hydrogen distribution device, the device can effectively disperse hydrogen into micron-sized small microbubbles and improve the reaction efficiency.
(2) In investment aspect: compared with the traditional hydrogenation technology, the method saves 10 to 50 percent; the high-grade lubricating oil base oil can generate higher profit value as a high value-added product.
(3) The operation cost is as follows: compared with the traditional hydrogenation technology, the method saves 25%; the load of the heating furnace is greatly reduced; the hydrogen loss amount is less; the maintenance cost of the device is lower; the catalyst dosage is lower, and the actual operation life is prolonged.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (11)
1. A method for hydroprocessing waste plastics, characterized by comprising the steps of:
s1, adding the waste plastics into a first liquid phase hydrogenation reactor to carry out hydrocracking reaction, wherein the hydrocracking reaction conditions are as follows: obtaining a cracking product at the pressure of 1-3MPa, the temperature of 500-700 ℃ and the time of 20-90 minutes;
s2, feeding the cracking product or the cracking product and an oil raw material into a second liquid phase hydrogenation reactor, and carrying out a hydroisomerization reaction, wherein the weight ratio of the cracking product to the Fischer-Tropsch wax is 1:0.5-3, and the conditions of the hydroisomerization reaction are as follows: the pressure is 10-15MPa, the temperature is 300-;
the oil raw material is selected from at least one of paraffin-based distillate oil and Fischer-Tropsch wax;
and S3, distilling or separating the isomeric product to obtain the lubricating oil base oil, the diesel oil and the hydrocarbon gas.
2. The method for hydrotreating waste plastic as defined in claim 1, wherein the temperature of the hydrocracking reaction is 550-650 ℃ and the temperature of the hydroisomerization reaction is 300-400 ℃.
3. The method of hydrotreating waste plastic of claim 1, characterized in that the catalyst for hydrocracking reaction is prepared from ZSM-5 molecular sieve and/or alumina.
4. Process for hydroprocessing waste plastics according to claim 1, characterized in that the support of the catalyst for the hydroisomerization reaction is a catalyst in a weight ratio of 10-20: 80-90 is prepared by mixing alumina and molecular sieve and extruding the mixture into strips, wherein the molecular sieve is at least one of ZSM-22, ZSM-23, ZSM-48 and SAPO-11.
5. The method of hydrotreating waste plastic of claim 1 wherein the first liquid-phase hydrogenation reactor is a thermal cracking reactor, the thermal cracking reactor being one selected from the group consisting of a tank reactor, a fixed bed reactor and a fluidized bed reactor.
6. A process for hydroprocessing waste plastics according to claim 1, characterized in that the second liquid phase hydrogenation reactor is a hydroisomerization reactor.
7. The method of hydrotreating waste plastic as claimed in claim 1, wherein the lubricating oil base oil has VI of not less than 120 and pour point of not more than-15 ℃.
8. An apparatus for hydroprocessing waste plastics, which is an apparatus used in the method of any one of claims 1 to 7, characterized by comprising: the hydrogen supply device is a hydrogen compressor, the hydrotreating unit consists of an oil-gas mixing device and a liquid-phase hydrogenation reactor, and the oil-gas mixing device and the liquid-phase hydrogenation reactor are respectively and independently connected with the hydrogen compressor.
9. The apparatus for hydroprocessing waste plastics according to claim 8, wherein the liquid-phase hydrogenation reactor comprises a first liquid-phase reactor and a second liquid-phase reactor.
10. The apparatus for hydroprocessing waste plastics according to claim 8, wherein the first liquid-phase hydrogenation reactor is a thermal cracking reactor selected from one of a tank reactor, a fixed bed reactor and a fluidized bed reactor.
11. An apparatus for hydroprocessing waste plastics according to claim 8, characterized in that the second liquid phase hydrogenation reactor is a hydroisomerization reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595959.9A CN111363580A (en) | 2018-12-25 | 2018-12-25 | Method and device for hydrotreating waste plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595959.9A CN111363580A (en) | 2018-12-25 | 2018-12-25 | Method and device for hydrotreating waste plastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111363580A true CN111363580A (en) | 2020-07-03 |
Family
ID=71202348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811595959.9A Pending CN111363580A (en) | 2018-12-25 | 2018-12-25 | Method and device for hydrotreating waste plastic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111363580A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708439A (en) * | 2020-12-25 | 2021-04-27 | 中化泉州石化有限公司 | Method for producing ethylene raw material |
| CN114276835A (en) * | 2021-12-24 | 2022-04-05 | 中化泉州石化有限公司 | Preparation method of base oil |
| CN117801838A (en) * | 2023-12-29 | 2024-04-02 | 上海菲利科思新材料有限公司 | Waste plastic hydro-thermal cracking and hydrofining method |
| CN117946742A (en) * | 2022-10-31 | 2024-04-30 | 中国石油化工股份有限公司 | Method for producing steam cracking raw material from waste plastics |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003089545A1 (en) * | 2002-04-18 | 2003-10-30 | Chevron U.S.A. Inc. | Process for converting waste plastic into lubricating oils |
| CN101932687A (en) * | 2007-12-27 | 2010-12-29 | 雪佛龙美国公司 | Process for preparing a pour point depressing lubricant base oil component from waste plastic and use thereof |
| CN103328619A (en) * | 2011-01-18 | 2013-09-25 | 雪佛龙美国公司 | Process for making high viscosity index lubricating base oils |
| CN105602619A (en) * | 2015-12-18 | 2016-05-25 | 中国石油天然气股份有限公司 | Liquid-phase hydrogenation isomerization system and process and application thereof |
| CN106795443A (en) * | 2014-07-17 | 2017-05-31 | 沙特基础全球技术有限公司 | In hydropyrolysis process poor hydrogen stream is modified using hydrogen donor stream |
-
2018
- 2018-12-25 CN CN201811595959.9A patent/CN111363580A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003089545A1 (en) * | 2002-04-18 | 2003-10-30 | Chevron U.S.A. Inc. | Process for converting waste plastic into lubricating oils |
| CN101932687A (en) * | 2007-12-27 | 2010-12-29 | 雪佛龙美国公司 | Process for preparing a pour point depressing lubricant base oil component from waste plastic and use thereof |
| CN103328619A (en) * | 2011-01-18 | 2013-09-25 | 雪佛龙美国公司 | Process for making high viscosity index lubricating base oils |
| CN106795443A (en) * | 2014-07-17 | 2017-05-31 | 沙特基础全球技术有限公司 | In hydropyrolysis process poor hydrogen stream is modified using hydrogen donor stream |
| CN105602619A (en) * | 2015-12-18 | 2016-05-25 | 中国石油天然气股份有限公司 | Liquid-phase hydrogenation isomerization system and process and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708439A (en) * | 2020-12-25 | 2021-04-27 | 中化泉州石化有限公司 | Method for producing ethylene raw material |
| CN112708439B (en) * | 2020-12-25 | 2022-10-04 | 中化泉州石化有限公司 | Method for producing ethylene raw material |
| CN114276835A (en) * | 2021-12-24 | 2022-04-05 | 中化泉州石化有限公司 | Preparation method of base oil |
| CN117946742A (en) * | 2022-10-31 | 2024-04-30 | 中国石油化工股份有限公司 | Method for producing steam cracking raw material from waste plastics |
| CN117946742B (en) * | 2022-10-31 | 2025-01-03 | 中国石油化工股份有限公司 | Method for producing steam cracking raw material from waste plastics |
| CN117801838A (en) * | 2023-12-29 | 2024-04-02 | 上海菲利科思新材料有限公司 | Waste plastic hydro-thermal cracking and hydrofining method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101679426B1 (en) | A method of preparing high graded lube base oil using unconverted oil | |
| US20080132435A1 (en) | Process to obtain biolubricants and bioparaffins by hydroprocessing mixtures of wax obtained from renewable resources and waxes of mineral origin | |
| CN101348732B (en) | Heavy distillate oil hydrotreating method | |
| CN111363580A (en) | Method and device for hydrotreating waste plastic | |
| CN105602619B (en) | Liquid-phase hydrogenation isomerization system and process and application thereof | |
| CN104080891A (en) | Process for making high VI lubricating oils | |
| CN101517038A (en) | Method for the hydro-processing of a gas oil feedstock, and corresponding hydro-refining unit | |
| CN110016363B (en) | Method and system for processing Fischer-Tropsch synthetic oil to produce diesel and lubricating oil base oil | |
| CN104004541B (en) | A kind of preparation method of coal-based high arene underwater content stock oil | |
| CN103773486A (en) | Combination method for raising yields of high-value products | |
| CN105713662A (en) | Hydrotreating and catalytic cracking combined process | |
| CN110616083B (en) | Process for producing crude white oil | |
| CN104277878B (en) | A kind of two-stage slurry state bed hydroprocessing technique of high temperature coal-tar | |
| CN100457862C (en) | One-step hydrogenation method for producing super white oil | |
| CN114437804B (en) | Hydrocracking method of high-nitrogen raw oil | |
| CN114437791B (en) | Low-pressure long-period hydrocracking process for Fischer-Tropsch synthetic oil | |
| CN110540873B (en) | Method for processing naphthenic oil | |
| CN111378495B (en) | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil | |
| CN111378494B (en) | Processing method of Fischer-Tropsch synthetic oil | |
| CN103102947A (en) | Production method for high-viscosity index lubricant base oil | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process | |
| CN114437789A (en) | Method for producing jet fuel from diesel oil fraction | |
| CN106675642B (en) | A kind of production method of low-coagulation diesel oil | |
| CN109988630B (en) | Wax oil hydrogenation method and system | |
| CN109988646B (en) | Wax oil hydrotreating and hydrofining combined process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200703 |
|
| RJ01 | Rejection of invention patent application after publication |