阅读说明：本技术 一种油和有机废物混合物的加工方法 (Method for processing mixture of oil and organic waste ) 是由 刘哲 王鑫 昝大鑫 吕云飞 邓宏达 于 2020-07-17 设计创作，主要内容包括：本申请公开了一种油和有机废物混合物的加工方法,涉及有机废物回收处理领域。本申请所述的加工方法包括以下步骤：混料；液相加氢,对加氢混合物进行液相加氢反应,液相加氢反应的的压力为50-250bar,液相加氢反应的反应温度为300-500℃,氢油比为100-1500标立/吨油。本申请通过将旧油、废油或废料混入基于石油的渣油或重油中作为加氢原料,通过加氢反应生产成品油,成品油的性质基本上取决于渣油中的产品,解决了旧油、废油或废料中油和有机废物混合物处理工艺复杂的问题,同时避免了将旧油、废油或废料处置于堆放场或通过热燃烧工艺时产生的环境污染问题。(The application discloses a processing method of a mixture of oil and organic waste, and relates to the field of organic waste recycling treatment. The processing method comprises the following steps: mixing materials; liquid phase hydrogenation, namely performing liquid phase hydrogenation reaction on the hydrogenation mixture, wherein the pressure of the liquid phase hydrogenation reaction is 50-250bar, the reaction temperature of the liquid phase hydrogenation reaction is 300-500 ℃, and the hydrogen-oil ratio is 100-1500 normal/ton oil. The present application solves the problem of complicated process for treating a mixture of oil and organic waste in old oil, waste oil or waste material by mixing the old oil, waste oil or waste material into petroleum-based residual oil or heavy oil as a hydrogenation raw material and producing a finished oil through hydrogenation reaction, the properties of the finished oil being substantially determined by the products in the residual oil, while avoiding the problem of environmental pollution caused when the old oil, waste oil or waste material is placed in a yard or is subjected to a thermal combustion process.)

1. A method for processing a mixture of oil and organic waste, comprising the steps of:

mixing materials: preparing a hydrogenation mixture comprising:

a. heavy oil, residual oil, or a mixture of both;

b. used oil, waste oil, or a mixture of the two; and/or

c. Organic waste or mixtures containing natural or synthetic organic compounds comprising uncrosslinked or crosslinked carbon chains;

and liquid phase hydrogenation, wherein the liquid phase hydrogenation reaction is carried out on the hydrogenation mixture, the pressure of the liquid phase hydrogenation reaction is 50-250bar, the reaction temperature of the liquid phase hydrogenation reaction is 300-500 ℃, and the hydrogen-oil ratio is 100-1500 normal/ton oil.

2. The method for processing the mixture of oil and organic waste as claimed in claim 1, wherein the raw material of the component b is one or more of solid polychlorinated biphenyl or halogen-containing waste oil, transformer oil, hydraulic oil, waste oil, under-cabin oil and tank cleaning residue.

3. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein the feedstock for component c is one or more of municipal sludge, paint sludge, halogen-containing solvents or distillation residues thereof, recycled process solvents, organic residues from chemical cleaning plants, organic residues from degreasing of parts or cleaning tanks, plastics or waste from the production of used plastics or plastics.

4. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein said component b and/or said component c is mixed with said component a in a mixer to form a hydrogenated mixture.

5. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein the weight ratio between component a and component b is from 100:1 to 1: 1.

6. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein the weight ratio between said component a and said component c is from 100:1 to 1: 1.

7. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein the weight ratio between said component a and said mixture of component b and said component c is from 100:1 to 1: 1.

8. The method of processing a mixture of oil and organic waste as in claim 1, wherein the liquid phase air entrainment reaction is carried out in a liquid phase hydrogenation reactor.

9. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein, in said blending step, an auxiliary agent is added to promote the reaction, the amount of the auxiliary agent added being 0.1-10 wt% of the hydrogenated mixture.

10. The method of claim 9, wherein the additive is a high surface area porous solid comprising one or more of carbon, ferric sulfate, ferric oxide, electrostatic filter dust, and cyclone dust.

11. A method of processing a mixture of oil and organic waste as claimed in claim 9 wherein said adjunct has a continuous particle size distribution with an average particle size of not less than 100 microns.

12. The method as claimed in claim 9, wherein the additives have a distinct particle size difference and are classified into a fine additive and a coarse additive according to a particle size range, the fine additive has a particle size of 90 μm or less, and the coarse additive has a particle size of 100-2000 μm.

13. A method of processing a mixture of oil and organic waste as claimed in claim 12 wherein said crude adjuvant comprises greater than or equal to 20% by weight of said adjuvant.

14. A method of processing a mixture of oil and organic waste as claimed in claim 1 wherein when said component c is added as sewage sludge, the weight ratio of said component a to said component c is preferably 10:1 to 1: 1.

15. The method of claim 14, wherein the sewage sludge has an average particle size of greater than or equal to 100 microns.

16. A method of processing a mixture of oil and organic waste as claimed in claim 14 wherein the sewage sludge is pre-dried to a water content of less than 10.0 wt% prior to blending.

17. A method of processing a mixture of oil and organic waste as claimed in claim 14 wherein the sludge is subjected to grinding, sieving or sieving to remove large foreign matter prior to blending.

18. The method of claim 1, wherein the hydrogenated mixture is mixed with pulverized coal in a ratio of 20:1 to 1: 1.

19. The method of claim 18, wherein the pulverized coal has a particle size of 100 μm or more.

20. The method of claim 1, wherein the product of the liquid phase hydrogenation reaction is separated in a hot separator to obtain a first fraction comprising unconverted fraction of heavy oil and residual oil and solids and a second fraction comprising reaction products in the vapor phase.

21. The method as claimed in claim 20, wherein the first separated substance flows out from the bottom of the hot separator, is heated by the third heating furnace and flows into the vacuum tower, the wax oil is recovered, and the residual hydrogenation residue is discharged from the bottom of the vacuum tower.

22. The method for processing the mixture of oil and organic waste as claimed in claim 20, wherein the second separator is discharged from the top of the hot separator and then sent to a gas phase hydrogenation reactor for gas phase hydrogenation.

23. A method of processing a mixture of oil and organic waste as claimed in claim 20 wherein the second fraction is cooled and condensed sufficiently to separate the gases and liquids in the second fraction in a separator.

24. A method of processing a mixture of oil and organic waste as claimed in claim 23, wherein the separated liquid product is taken from the bottom of the separator and a stripper is used to separate the light components including C from the top of the column₁-C₄、H₂、H₂S; and heating the material at the bottom of the stripping tower in a second heating furnace, and then sending the heated material into a fractionating tower to fractionate gasoline, diesel oil and wax oil components.

25. A method of processing a mixture of oil and organic waste as claimed in claim 23 wherein the separated gaseous product comprises C₁-C₄Gas, H₂S、NH₃And hydrogen halide, and discharging water-soluble components in the hydrogen halide along with the wastewater.

26. An apparatus for processing a mixture of oil and organic waste, characterized in that a method for processing a mixture of oil and organic waste as claimed in any one of claims 1 to 25 is used.

27. A diesel fuel, characterized in that it is produced using a method for processing a mixture of oil and organic waste as defined in any one of claims 1 to 25 or an apparatus for processing a mixture of oil and organic waste as defined in claim 26.

28. A gasoline produced by a method of processing an oil and organic waste mixture according to any one of claims 1 to 25 or an apparatus for processing an oil and organic waste mixture according to claim 26.

29. A wax oil produced by a method of processing an oil and organic waste mixture according to any one of claims 1 to 25 or an apparatus for processing an oil and organic waste mixture according to claim 26.

Technical Field

The application relates to the field of organic waste recovery and treatment, in particular to a method for processing a mixture of oil and organic waste.

Background

Disclosure of Invention

The application aims to provide a processing method for mixing oil and organic waste, which solves the problem that the processing flow of the mixture of the oil and the organic waste is complex in the prior art, optimizes the processing flow, reduces the production cost and reduces the influence on the environment.

In order to achieve the above purpose, the embodiments of the present application adopt the following technical solutions: a method of processing a mixture of oil and organic waste, comprising the steps of:

mixing materials: preparing a hydrogenation mixture comprising:

a. heavy oil, residual oil, or a mixture of both;

b. used oil, waste oil, or a mixture of the two; and/or

c. Organic waste or mixtures containing natural or synthetic organic compounds comprising uncrosslinked or crosslinked carbon chains;

liquid phase hydrogenation, namely performing liquid phase hydrogenation reaction on the hydrogenation mixture, wherein the pressure of the liquid phase hydrogenation reaction is 50-250bar, the reaction temperature of the liquid phase hydrogenation reaction is 300-500 ℃, and the hydrogen-oil ratio is 100-1500 normal/ton oil.

In the above technical solution, in the embodiments of the present application, the old oil, the waste oil, or the waste material is mixed into the petroleum-based residual oil or the heavy oil as a hydrogenation raw material, and the product oil is produced through a hydrogenation reaction, and the properties of the product oil substantially depend on the products in the residual oil, thereby solving the problem of a complex process for treating the mixture of the oil and the organic waste in the old oil, the waste oil, or the waste material, and simultaneously avoiding the problem of environmental pollution caused when the old oil, the waste oil, or the waste material is placed in a yard or is subjected to a thermal combustion process.

Further, according to the embodiment of the application, the raw material of the component b is one or more of solid waste oil containing polychlorinated biphenyl or halogen, transformer oil, hydraulic oil, waste oil, under-cabin oil and oil tank cleaning residue.

Further, according to the embodiments of the present application, wherein the raw material of component c is one or more of municipal sludge, paint sludge, halogen-containing solvent or distillation residue thereof, recycled process solvent, organic residue of chemical cleaning plant, organic residue in degreasing of parts or cleaning tank, plastic or waste generated in used plastic or plastic production.

Further, according to the examples herein, component b and/or component c are mixed with component a in a mixer to form a hydrogenated mixture.

Further, according to the embodiment of the application, the weight ratio of the component a to the component b is 100:1-1: 1.

Further, according to the embodiment of the application, the weight ratio of the component a to the component c is 100:1-1: 1.

Further, according to the embodiment of the application, the weight ratio of the component a to the mixture of the component b and the component c is 100:1-1: 1.

Further, according to the embodiment of the present application, the liquid phase gas filling reaction is performed in a liquid phase hydrogenation reactor.

Further, according to the embodiment of the present application, wherein in the material mixing step, an auxiliary agent is added for promoting the reaction, the addition amount of the auxiliary agent is 0.1-10 wt% of the hydrogenation mixture.

Further, according to the embodiments of the present application, the auxiliary agent is a high-surface-area porous solid including one or more of carbon, ferric sulfate, ferric oxide, electrostatic filter dust, and cyclone dust.

Further in accordance with embodiments herein, wherein the adjuvant has a continuous particle size distribution, the average particle size is not less than 100 microns.

Further, according to the embodiments of the present application, the additives have a distinct particle size difference, and can be divided into a fine additive and a coarse additive according to the particle size range, wherein the particle size of the fine additive is 90 microns or less, and the particle size of the coarse additive is 100-2000 microns.

Further, according to the embodiment of the application, the proportion of the crude auxiliary agent in the auxiliary agent is more than or equal to 20 wt%.

Further, according to the embodiment of the present application, wherein when the component c is sewage sludge, the weight ratio of the component a to the component c is preferably 10:1 to 1: 1.

Further, according to the embodiment of the present application, wherein the average particle size of the sewage sludge is greater than or equal to 100 micrometers.

Further, according to the embodiment of the application, before mixing, the sewage sludge is dried in advance until the water content is less than 10.0 wt%.

Further, according to the embodiment of the present application, before mixing, the sludge is subjected to grinding, sieving or sieving to remove large foreign matters.

Further, according to the examples of the present application, wherein the hydrogenated mixture is mixed with pulverized coal in a ratio of 20:1 to 1: 1.

Further, according to the embodiment of the application, the particle size of the coal powder is greater than or equal to 100 microns.

Further, according to the embodiment of the present application, the product of the liquid phase hydrogenation reaction enters a hot separator for separation, and a first separated matter and a second separated matter are obtained, wherein the first separated matter comprises the unconverted part of the heavy oil and the residual oil and the solid, and the second separated matter is the reaction product of the gas phase.

Further, according to the embodiment of the application, the first separated substance flows out from the bottom of the hot separator, is heated by the third heating furnace and flows into the vacuum tower, the wax oil in the vacuum tower is recovered, and the residual hydrogenation residue is discharged from the bottom of the vacuum tower.

Further, according to the embodiment of the present application, after the second separator flows out from the top of the hot separator, the second separator may be sent to a gas phase hydrogenation reactor for gas phase hydrogenation.

Further, according to the embodiment of the present application, after the second separated object is sufficiently cooled and condensed, the gas and the liquid in the second separated object are separated in the separator.

Further, according to the embodiment of the present application, wherein the separated liquid product flows out from the bottom of the separator, and the light component is separated from the top of the tower through the stripping tower, wherein the light component comprises C₁-C₄、H₂、H₂S; and heating the material at the bottom of the stripping tower in a second heating furnace, and then sending the heated material into a fractionating tower to fractionate gasoline, diesel oil and wax oil components.

Further in accordance with an embodiment of the present application, wherein the separated gas product comprises C₁-C₄Gas, H₂S、NH₃And hydrogen halide, and discharging water-soluble components in the hydrogen halide along with the wastewater.

In order to achieve the purpose, the embodiment of the application also discloses equipment for processing the mixture of the oil and the organic waste, and the processing method of the mixture of the oil and the organic waste is adopted.

In order to achieve the purpose, the embodiment of the application also discloses diesel oil which is prepared by adopting the processing method of the oil and organic waste mixture or the processing equipment of the oil and organic waste mixture.

In order to achieve the above object, the present application also discloses a gasoline produced by using a method for processing a mixture of oil and organic waste as described above or an apparatus for processing a mixture of oil and organic waste as described above.

In order to achieve the purpose, the embodiment of the application also discloses a wax oil which is prepared by adopting the processing method of the oil and organic waste mixture or the processing equipment of the oil and organic waste mixture.

Compared with the prior art, the method has the following beneficial effects: the present application solves the problem of complicated process for treating a mixture of oil and organic waste in old oil, waste oil or waste material by mixing the old oil, waste oil or waste material into petroleum-based residual oil or heavy oil as a hydrogenation raw material and producing a finished oil through hydrogenation reaction, the properties of the finished oil being substantially determined by the products in the residual oil, while avoiding the problem of environmental pollution caused when the old oil, waste oil or waste material is placed in a yard or is subjected to a thermal combustion process.

Drawings

The present application is further described below with reference to the drawings and examples.

FIG. 1 is a process for processing oil and organic waste in this application.

In the attached drawings

1. Blender 2, high-pressure pump 3, new hydrogen machine

4. Heating furnace I5, liquid phase hydrogenation reactor 6 and heat separator

7. Separator 8, stripping tower 9 and heating furnace II

10. Fractionating tower 11, membrane separator 12, and hydrogen circulation machine

13. Heating furnace III 14, decompression tower 15 and circulating hydrogen pipeline

16. Cold hydrogen pipe

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clear and fully described, embodiments of the present invention are further described in detail below with reference to the accompanying drawings. It is to be understood that the specific embodiments described herein are merely illustrative of some embodiments of the invention and are not limiting of the invention, and that all other embodiments obtained by those of ordinary skill in the art without the exercise of inventive faculty are within the scope of the invention.

In the description of the present invention, it should be noted that the terms "center", "middle", "upper", "lower", "left", "right", "inner", "outer", "top", "bottom", "side", "vertical", "horizontal", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "a," "an," "first," "second," "third," "fourth," "fifth," and "sixth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

For the purposes of simplicity and explanation, the principles of the embodiments are described by referring mainly to examples. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments. It will be apparent, however, to one skilled in the art that the embodiments may be practiced without these specific details. In some instances, well-known methods and structures have not been described in detail so as not to unnecessarily obscure the embodiments. In addition, all embodiments may be used in combination with each other.

As shown in fig. 1, the present application discloses a method for processing a mixture of oil and organic waste, comprising the steps of:

mixing materials: preparing a hydrogenation mixture comprising:

a. heavy oil, residual oil, or a mixture of both;

b. used oil, waste oil, or a mixture of the two; and/or

c. Organic waste or mixtures containing natural or synthetic organic compounds comprising uncrosslinked or crosslinked carbon chains;

liquid phase hydrogenation, wherein the hydrogenation mixture is subjected to liquid phase hydrogenation reaction, the pressure of the liquid phase hydrogenation reaction is 50-250bar, the reaction temperature of the liquid phase hydrogenation reaction is 300-500 ℃, and the hydrogen-oil ratio is 100-1500 normal/ton oil.

In the technical scheme, the method produces the finished oil through the hydrogenation reaction by mixing the old oil, the waste oil or the waste material into the residual oil or the heavy oil based on petroleum as the hydrogenation raw material, wherein the properties of the finished oil basically depend on products in the residual oil, so that the problem of complex treatment process of the mixture of the oil and the organic waste in the old oil, the waste oil or the waste material is solved, and the problem of environmental pollution caused by placing the old oil, the waste oil or the waste material in a stacking yard or through a hot combustion process is avoided.

Wherein, the raw material of the component b is one or more of solid waste oil containing polychlorinated biphenyl or halogen, transformer oil, hydraulic oil, waste oil, tank bottom oil and cleaning residue of an oil tank; the raw material of component c is one or more of municipal sludge, paint sludge, halogen-containing solvent or distillation residue thereof, recycled process solvent, organic residue of a chemical cleaning plant, organic residue in degreasing of parts or cleaning tanks, plastics or waste generated in the production of used plastics or plastics.

Component b and/or component c is mixed with component a in a mixer 1 to form a hydrogenation mixture, the weight ratio between component a and component b, between component a and component c or between component a and the mixture of component b and component c being 100:1 to 1: 1.

The liquid phase air entrainment reaction is carried out in a liquid phase hydrogenation reactor 5, and the liquid phase hydrogenation reactor 5 consists of 2-4 vertically arranged empty reactors connected in series. The liquid-phase hydrogenation reactor 5 is communicated with the mixer 1, and the hydrogenation mixture mixed in the mixer 1 is pressurized by the high-pressure pump 2 and then is sent to the liquid-phase hydrogenation reactor 5. A heating furnace 4 is arranged between the liquid phase hydrogenation reactor 5 and the high pressure pump 2, and before entering the heating furnace 4, the hydrogenation mixture is mixed with the fresh hydrogen fed by the new hydrogen machine 3. Wherein the reaction temperature in the liquid phase hydrogenation reactor is 350-500 ℃, preferably 400-490 ℃, and the reaction pressure is 50-250bar, preferably 100-200 bar.

The hydrogenation mixture is subjected to liquid phase hydrogenation reaction, and the method has the following advantages:

(1) under the condition of liquid phase hydrogenation, the hydrogenation reaction heat generated in the component a conversion process can be used for converting and purifying the component b and/or the component c, and additional heat energy is not required to be provided, so that the resource is saved;

(2) the mixture of the petroleum-based component a and the hydrogenation gas as a 'carrier' component has better fluid stability, so that the waste solids in the component b and/or the component c can flow in a reaction system based on the characteristic, and the reaction system is more suitable for a liquid phase hydrogenation reactor;

(3) the product oil generated in the hydrotreating process can be further processed by utilizing the existing refinery device to prepare an oil product which can be directly sold, so that economic benefit is obtained;

(4) the above-described processing method can be used for treating waste oils or wastes classified as special wastes, while being able to retain the carbon, in particular hydrocarbon chains, contained in these raw materials;

(5) the above-described process allows the heteroatoms, in particular oxygen, sulphur, nitrogen and halogens, present in the raw material to be eliminated extensively, converted into the corresponding hydrogen compounds, introduced into the gaseous phase and discharged as waste water, together with the hydrogen halide and the ammonia and partially or totally dissolved hydrogen sulphide present therein.

In the technical scheme, an auxiliary agent can be added for promoting the reaction during material mixing, the addition amount of the auxiliary agent is 0.1-10 wt% of the hydrogenation mixture, and a porous solid with a high surface area can be selected and used, and the porous solid comprises one or more of carbon, ferric sulfate, ferric oxide, electrostatic filtering dust and cyclone dust. Wherein, the auxiliary agent can be divided into a fine auxiliary agent and a coarse auxiliary agent according to the particle size range, the fine auxiliary agent is used when the particle size is 90 microns or less, and the coarse auxiliary agent is used when the particle size is 100-2000 microns.

Specifically, when a carbon-containing high surface area promoter is used in the liquid phase hydrogenation, the promoter is preferably added in an amount of 0.1 to 10 wt%, more preferably 0.5 to 5.0 wt%. The carbonaceous high surface auxiliary agent preferably uses brown coal coke from blast furnaces and hearth furnaces, carbon black from heavy oil gasification, anthracite, lignite, and activated carbon, petroleum coke and coal gasification dust produced therefrom. Among these, the carbon-containing high surface area assistants used are preferably obtained by impregnation with the metal salt solutions, it being possible to use metals of transition groups 1 to 8 and main group 4 of the periodic Table of the elements, preferably iron, cobalt, nickel, vanadium or molybdenum. The addition of a carbonaceous high surface area promoter in liquid phase hydrogenation is also beneficial to promoting the hydrodemetallization and hydrodesulfurization reactions.

Secondly, iron oxide, electrostatic filter dust and cyclone dust from metal or ore processing can also be used as auxiliaries, preferably in amounts of from 0.1 to 10% by weight, particularly preferably from 0.5 to 5.0% by weight. These components may be used as they are or after a pretreatment such as vulcanization.

In the above-described solutions, it is preferred to use auxiliaries having a marked particle size difference, but it is also possible to use auxiliaries having a continuous particle size distribution in which the average particle size of the corresponding large or coarse particle size fraction is not less than 100. mu.m. Preferably, two types of particles having different particle diameters are used as the aid, for example, a fine aid having a particle diameter of 90 microns or less (preferably 50 microns or less), and a coarse aid having a particle diameter in the range of 100-2000 microns (preferably 100-1000 microns). The two kinds of auxiliary agents with different particle sizes can be respectively added into the hydrogenation mixture, or can be added into the hydrogenation mixture after being premixed. The proportion of coarse promoter used may be 20 wt% or more of the promoter used and may include carbonaceous high surface area solids and iron oxides, electrostatic filter dust and cyclone dust, among others.

On this basis, the concentration of the crude auxiliary agent accumulated in the reaction system increases at the operation stage of the hydrogenation process. Therefore, the amount of the crude auxiliary added may be gradually reduced as the reaction proceeds (i.e., the amount may be less than 20 wt%), as long as the total proportion of the crude auxiliary in the hydrogenation mixture is ensured to be equal to or greater than 20 wt%.

Furthermore, the component c to be added often contains solid waste, such as large-particle-size sludge in sewage sludge, coarse particles in waste, etc., and may replace a part of the coarse auxiliary agent of the auxiliary agent. Wherein, when the added component c is sewage sludge, the weight ratio of the component a to the component c is preferably 10:1-1:1, and correspondingly, the average grain diameter of the sludge is more than or equal to 100 microns. The sludge is dried to a water content of less than 10.0 wt.%, preferably less than 2.0 wt.%. If desired, it is also possible to remove large foreign substances by grinding, sieving or sieving and to make the particle size smaller than 1.0mm, preferably smaller than 0.5mm, and the sewage sludge treated in this way can partly or completely replace the above-mentioned auxiliaries.

Furthermore, the above-mentioned hydrogenated mixture may be mixed with pulverized coal in a ratio of 20:1 to 1:1, preferably in a ratio of 5:1 to 5: 4. This is due to the fact that in the hydroconversion of mixtures of heavy (or residual) and old (or waste) oils, the cotransformation, in combination with the above mentioned other raw materials, such as organic waste oils, can be achieved in the presence of lignite or anthracite, the oil to coal weight ratio preferably being 5: 1-1: 1. coal powder having a particle size of 100 μm or more may be used as the aid according to the ratio of the large particle aid to be added as needed.

When the component b and/or the component c to be added contain a halogen component, hydrogen halide is formed during the hydrogenation. A neutralizing agent may be added to the hydrogenation mixture to neutralize the hydrogen halide formed: although any neutralizing agent that reacts efficiently with hydrogen halide can be used, alkali and alkaline earth metal sulfides and hydroxides are preferred as neutralizing agents, and sodium sulfide is a particularly preferred neutralizing agent. The neutralizing agent may be added as a solid, an aqueous solution or a suspension in oil, preferably 0.01 to 5.0 wt.%. Among these, a particularly preferred embodiment is to add sodium sulfide to the aqueous solution. The neutralizing compound is preferably injected together with water at a suitable point at the outlet of the liquid phase reactor and can be discharged from the process system as an aqueous solution of the corresponding halide, for example by phase separation in a so-called cold separator.

In summary, the type and amount of consumable adjuvant can be selected based on the desired conversion and the tendency of the starting material to form coke.

In addition, the product of the liquid phase hydrogenation reaction flows out from the top of the liquid phase hydrogenation reactor 5 and then enters a thermal separator 6 for separation, so that a first separator and a second separator are obtained, wherein the first separator comprises the unconverted part of heavy oil and residual oil and solid, and the second separator is a gas phase reaction product. The hot separator 6 operates at approximately the same temperature and pressure as the liquid phase hydrogenation reactor 5.

The specific composition and content of the solids contained in the first fraction depend on the type of feedstock, for example, if the waste material comprises waste oil or sludge containing solids, the residue will contain a large amount of ash and heavy metals, and these components are converted into a more easily handled state after liquid phase hydrogenation than in the starting feedstock. Furthermore, the metals and ash-forming components are enriched in the hot separator residue, also making them recoverable by, for example, metallurgical processes.

In addition, the first separated substance flows out from the bottom of the hot separator 6, is heated by the third heating furnace 13 and then flows into the vacuum tower 14, the wax oil in the first separated substance is recovered, and the residual hydrogenation residue is discharged from the bottom of the vacuum tower 14.

The second separated material flowing out from the top of the hot separator 6 may be sent to a gas phase hydrogenation reactor (not shown in the figure) for gas phase hydrogenation reaction. The gas phase hydrogenation reactor is a fixed bed reactor and contains a hydrotreating or mild hydrocracking catalyst, and the reaction conditions are the same as the liquid phase hydrogenation pressure. The gas phase hydrogenation reaction is carried out, under the action of a catalyst, hydrofining and hydrocracking are carried out, impurities are removed, and the liquid phase reaction product oil can be further processed into marketable gasoline and diesel oil.

The second separator thus obtained is cooled and condensed sufficiently, and the gas and liquid therein are separated in a separator 7, the separator 7 being a high pressure cold separator. After separation, the liquid product flows out from the bottom of the separator 7, and the light components, mainly comprising C, are separated from the top of the column by a stripping column 8₁-C₄、H₂、H₂S and the like. And heating the bottom material of the stripping tower by a second heating furnace 9, and then sending the bottom material into a fractionating tower 10 to fractionate gasoline, diesel oil and wax oil components.

The gaseous product separated off generally comprises C₁-C₄Gas, H₂S、NH₃Hydrogen halide, etc., which are enriched in the process gas, so that water-soluble components can be discharged together with the waste water, and due to C₁-C₄The gas is separated according to its solubility, preferably by washing with oil. The hydrogen remaining in the process gas is returned to the front end liquid phase hydrogenation reactor and the gas phase hydrogenation reactor as recycle hydrogen by the hydrogen recycle machine 12. And part of the circulating hydrogen is discharged as purge gas, so that the purity of the hydrogen of the circulating hydrogen is ensured to be more than 80 mol%. This purge gas may be passed through a membrane separator 11 to separate impurities and the recovered hydrogen may be recycled to the reaction system as fresh hydrogen. The hydrogen circulating machine 12 is communicated with the inlet of the first heating furnace 4 through a circulating hydrogen pipeline 15, so that circulating hydrogen and new hydrogen are mixed with the raw materials. In addition, the reaction temperature is controlled by injecting quench gas (fresh hydrogen or circulating hydrogen) into the liquid phase hydrogenation reactor 5 through the cold hydrogen pipe 16, so that the liquid phase hydrogenation reactor 5 operates under an isothermal condition.

The technical means of the present application will be described below with reference to examples 1 to 4, but the present application is not limited thereto.

[ EXAMPLES one ]

In a continuously operated hydrogenation system with three continuous vertical liquid phase hydrogenation reactors and no internals, a hydrogenation mixture having the following composition is charged:

a. vacuum residua of Arabian light crude oil;

c. sewage sludge, the addition amount of which is 10 wt% of the component a, the sewage sludge is dried to residual moisture of less than 2.0 wt%, and the sewage sludge is ground and sieved until the particle size is less than 150 microns.

The hydrogenation mixture was also supplemented with 2 wt% brown coal coke, the upper limit of particle size being 40 microns.

In the liquid phase hydrogenation reactor, 1.5 cubic meters of hydrogen is consumed for converting one kilogram of residual oil, and the hydrogen partial pressure is 190 bar. To achieve 90% bottoms conversion, the liquid phase reactor was set to have an average temperature of 465 ℃.

The reaction results of this example are shown in table 1 below.

TABLE 1

[ example two ]

In a liquid phase reactor hydrogenation plant with continuous operation, a hydrogenation mixture having the following composition is charged:

a. vacuum residuum of middle east crude oil;

c. used industrial cleaning oil, the addition amount is 15 wt% of the component a; the addition amount of the sewage sludge is 15 wt%.

Wherein, the chlorine content of the industrial cleaning oil is 4 percent, the sewage sludge is dried until the residual moisture is less than 2 percent, and 90 percent of particles have the particle size of less than 90 microns and 10 percent of particles have the particle size of between 100 and 150 microns by crushing the sewage sludge.

In the liquid phase hydrogenation reactor, the hydrogen partial pressure was 210bar and the reaction temperature was 470 ℃. Meanwhile, in order to neutralize HCl generated, Na was continuously added in an amount of 1 wt% with respect to the component a₂And S. After the reaction, 91.0% of the vacuum residue is converted into low boiling products, the chlorine content of the products is less than 1ppm (weight), and more than 76.0% of the organic part of the sewage sludge is converted into liquid products. The formation of hydrocarbon gases (C) relative to the residue used was observed₁-C4) was 8.2 wt%.

Specific results are shown in table 2.

TABLE 2

Operating conditions
		Temperature (liquid phase hydrogenation)	470℃
Hydrogen to oil ratio	850 normal/ton oil feed
		Sewage sludge	15 wt% oil feed
Na2S	1 wt% oil feed
		Product(s)
>500 ℃ oil (conversion)	91.0％
		C1–C4Qi (Qi)	8.2％
Conversion ratio of sewage sludge (organic matter part)	More than 76 percent

[ EXAMPLE III ]

In a continuously operated combined liquid/gas phase hydrogenation unit, a hydrogenation mixture having the following composition is charged:

a. arabian light vacuum residuum;

b. the addition amount of the degreasing solution of the waste metals is 30 wt% of the component a, the chlorine content of the degreasing solution containing aromatic and phenol is 1.02 wt%, the oxygen content is 3.7 wt%, the nitrogen content is 0.92 wt%, the sulfur content is 0.98 wt%, the content of the fraction at 0-200 ℃ is 44 wt%, and the content of the fraction at 200-350 ℃ is 22 wt%.

2 wt% of coke is added into the hydrogenation mixture as an auxiliary agent, wherein the particle size of 1.5 wt% of the auxiliary agent is less than 90 microns, and the particle size of 0.5 wt% of the auxiliary agent is 100-400 microns

In the reaction system, the hydrogen/oil ratio was 900 normal/ton oil and the hydrogen partial pressure was 200 bar. At 463 c, 90.7 wt% of the vacuum residue is converted to lower boiling products (below 500 c). The chlorine content in the main product of liquid phase hydrogenation is less than 1 ppm. Chlorine contained in the metal degreasing solution is separated in a hot separator into sodium chloride by adding twice the stoichiometric amount of sodium sulfide. The main product of liquid phase hydrogenation is in a direct combined gas phase hydrogenation reactor at 380 ℃ and the volume space velocity of 0.8h^-1Under the catalyst condition, sending the mixture to an industrial catalytic fixed bed for refining. After gas phase hydrogenation, all reaction products are free of phenol and chlorine, and the content of sulfur and nitrogen is less than 0.1 wt%. Specific results are shown in table 3.

TABLE 3

Operating conditions
		Temperature (liquid phase hydrogenation)	463℃
Hydrogen to oil ratio	900 normal/ton oil feed
		Auxiliary agent	2% by weight of oil feed
Na2S	2% by weight of oil feed
		Product(s)
>500 ℃ oil (conversion)	90.7％
		C1-C4 gas	9.3％

[ EXAMPLE IV ]

In a continuously operating liquid phase hydrogenation reactor unit, a hydrogenation mixture having the following composition is charged:

a. arabian light vacuum residuum;

b. the solid dirty oil-containing part with the addition amount of 10 wt% of the component a and more than 80 wt% of the solid dirty oil-containing organic matter part comprises the following components: 17 wt% ash, 54 wt% carbon, 6.5 wt% hydrogen, 0.2 wt% sulfur, the remaining components being nitrogen and oxygen.

In the embodiment, the added auxiliary agent is coal-based activated carbon accounting for 2 wt% of the component, wherein 75 wt% of particles with the particle size smaller than 90 microns are fine auxiliary agents, and 25 wt% of particles with the particle size of 100-550 microns are coarse auxiliary agents; the hydrogen/oil ratio was 900 normal/ton oil and the hydrogen partial pressure was 200 bar. At 460 c, 94.2 wt% of the vacuum residue was converted to lower boiling products, with the results shown in table 4.

TABLE 4

Operating conditions
		Temperature (liquid phase hydrogenation)	460℃
Hydrogen to oil ratio	800 normal/ton oil feed
		Auxiliary agent	2 wt% oil feed
Product(s)
		>500 ℃ oil (conversion)	94.2％
Waste lubricating oil organic matter (conversion rate)	80％
		C1-C4 gas	7.8％

Although the illustrative embodiments of the present application have been described above to enable those skilled in the art to understand the present application, the present application is not limited to the scope of the embodiments, and various modifications within the spirit and scope of the present application defined and determined by the appended claims will be apparent to those skilled in the art from this disclosure.