Method for reaction dechlorination of chlorine-containing oil products

Abstract

The present invention relates to the technical field of deep processing of oil products, and discloses a method for reaction dechlorination of chlorine-containing oil products. The method includes: (1) reacting the chlorine-containing oil product with an adsorbent so that at least part of the organic chlorine in the chlorine-containing oil product is converted into inorganic chlorine to obtain material W; (2) contacting material W with a dechlorination agent to obtain dechlorinated oil. This method can achieve a relatively high dechlorination rate and has the advantage of low cost.

Description

Technical Field

[0001] The present invention relates to the technical field of deep processing of oil products, and particularly relates to a method for reaction dechlorination of chlorine-containing oil products. Background Art

[0002] Chlorides in crude oil include two major categories: inorganic chlorides and organic chlorides. Inorganic chlorides are mainly various salts, such as NaCl, CaCl2, etc., which can be removed through the electro-de-salting process, and the harmful effects on existing refinery units are controllable; organic chlorides are mainly inherent in crude oil and various chlorine-containing compound additives added additionally during the extraction, treatment, and transportation of crude oil. Organic chlorides will react during the crude oil processing to generate chloride ions, resulting in chlorine corrosion problems, mainly including three aspects: acid corrosion, NH4Cl fouling blockage and under-fouling corrosion, and chloride ion stress corrosion cracking. In addition, it may also cause problems such as catalyst poisoning. Most refinery units may be affected by chlorine, and the harmful effects of organic chlorides, especially high-boiling organic chlorides, are greater. Therefore, it is necessary to strictly control the organic chlorine content in crude oil to protect refinery units. With the increasingly serious problems of heavy and inferior crude oil, the chlorine content in crude oil shows an increasing trend.

[0003] In addition, some oils from special sources, such as waste plastic pyrolysis oil, often contain Cl contents several times, dozens of times, or even hundreds of times higher than that of crude oil because the raw materials contain PVC products. The Cl content in some typical pyrolysis oils can reach 2000 μg / g, and the Cl content in medical waste pyrolysis oil can even reach 8000 μg / g. Such a high Cl content obviously cannot be deeply processed using existing refinery units, which severely limits the chemical recycling of waste plastics and the destination of the oils obtained from chemical recycling.

[0004] CN102127464A discloses a method for electro-de-salting and removing organic chlorine in crude oil. In this method, a demulsifier, an alkaline compound, a phase transfer agent, water, and oil products are mixed, and under the action of heat and an electric field, organic chlorine is converted into inorganic chlorine and transferred to the water phase, while oil-water separation is carried out simultaneously, so as to achieve the purpose of removing organic chlorine. However, this process requires the addition of a large amount of phase transfer agent and water, undoubtedly increasing the separation cost.

[0005] CN1539693A discloses a method for catalytic hydrogenation dechlorination of organic chlorine. Using a mixture of calcium oxide and iron oxide or a composite oxide of the two as a dechlorination agent, at a temperature above 200 °C, organic chlorine is converted into inorganic chlorine through catalytic hydrogenation, and then reacts with the dechlorination agent to achieve the purpose of dechlorination. This patent cannot handle oils with high organic chlorine content. At the same time, adopting a hydrogenation scheme requires a supporting hydrogen production device and consumes hydrogen. The hydrogenation agent is prone to poisoning, and the cost is relatively high.

[0006] US3864243 discloses a method for adsorptive removal of organic chlorine. In this method, zeolite molecular sieve is used to remove chlorides in oil products by adsorption. However, this method is a physical adsorption with low adsorption capacity, poor selectivity, and it is very easy to cause non-compliance of dechlorination when the operation fluctuates.

[0007] US5928500 provides a method using porous high-specific-surface silica as a carrier and metals or metal oxides such as Fe, Co, Ni and their mixtures as active components as an adsorbent. By converting organic chlorine into inorganic chlorine and reacting with metals in-situ, the method can remove organic chlorine. However, this method also has the problem of low adsorption capacity.

[0008] CN105368483A provides a catalytic conversion method for high-chlorine raw materials. In this method, high-chlorine raw materials are directly processed by catalytic cracking. After the organic chlorine is cracked, it is deposited on the catalyst in the form of inorganic salts. At the same time, the dechlorination efficiency is not high. For crude oil with 53 μg / g of chlorine, the dechlorination rate is only 78.92%. Obviously, this method is not suitable for dechlorination treatment of special oil products such as waste pyrolysis oil.

[0009] Based on this, there is an urgent need to develop an efficient and low-cost method for dechlorination of oils with high chlorine content. Summary of the Invention

[0010] The object of the present invention is to overcome the problems existing in the prior art and provide a method for reactive dechlorination of chlorine-containing oils. This method can achieve a relatively high dechlorination rate and has the advantage of low cost.

[0011] To achieve the above object, on the one hand, the present invention provides a method for reactive dechlorination of chlorine-containing oils, which includes:

[0012] (1) Reacting the chlorine-containing oil with an adsorbent so that at least part of the organic chlorine in the chlorine-containing oil is converted into inorganic chlorine to obtain a stream W;

[0013] (2) Contacting the stream W with a dechlorinating agent to obtain dechlorinated oil.

[0014] Preferably, the adsorbent and the dechlorinating agent are loaded in different beds of the same reactor. Along the direction of the stream, the adsorbent is located upstream of the dechlorinating agent.

[0015] Preferably, the volume ratio of the adsorbent to the dechlorinating agent is 1:0.25 - 4, preferably 1:0.66 - 1.5.

[0016] Preferably, the bed where the adsorbent is located is a constant temperature zone.

[0017] Preferably, the temperature of the constant temperature zone is 200 - 450 °C, preferably 380 - 400 °C.

[0018] Through the above technical solution, the beneficial effects of the present invention include:

[0019] The method of the present invention can achieve a relatively high dechlorination rate and has the advantage of low cost.

[0020] The method of the present invention enables the high-chlorine feedstock oil to meet the incoming plant standards for refining feedstock oil in existing refineries after treatment, thus broadening the source of feedstock oil. Description of the Drawings

[0021] Figure 1 is a flow chart of the method for reactive dechlorination of chlorine-containing oil products of the present invention.

[0022] Description of the Reference Numerals

[0023] 1, raw material storage tank; 2, oil pump; 3, adsorption reactor; 3.1, ceramic packing; 3.2, adsorbent bed layer; 3.3, dechlorination agent bed layer; 3.4, ceramic packing; 4, cooler; 5, oil-gas separator; 6, dechlorinated oil storage tank; 7, non-condensable gas. Detailed Embodiments

[0024] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0025] On the one hand, the present invention provides a method for reactive dechlorination of chlorine-containing oil products, which method includes:

[0026] (1) Reacting the chlorine-containing oil product with an adsorbent so that at least part of the organic chlorine in the chlorine-containing oil product is converted into inorganic chlorine to obtain material W;

[0027] (2) Contacting material W with a dechlorination agent to obtain dechlorinated oil.

[0028] In the prior art, the adsorbent generally performs dechlorination in the form of physical adsorption, having the defects of low adsorption capacity and low removal efficiency. In the method of the present invention, the organic chlorine in the chlorine-containing oil product first undergoes a chemical reaction with the adsorbent, so that at least part of the organic chlorine in the chlorine-containing oil product is converted into inorganic chlorine (HCl), with a relatively high conversion efficiency and without the need to consume additional hydrogen. Then, the inorganic chlorine (HCl) forms a stable chloride salt after contacting with the dechlorination agent, thereby achieving a relatively high dechlorination rate.

[0029] According to the present invention, preferably, the adsorbent and the dechlorinating agent are filled in different beds of the same reactor, and along the direction of the material flow, the adsorbent is located upstream of the dechlorinating agent. By adopting this preferred embodiment, the HCl formed in the adsorbent bed can react with the dechlorinating agent, preventing the addition reaction of HCl with olefins to reform organic chlorine due to its long-term residence at high temperature.

[0030] According to the present invention, preferably, the filling volume ratio of the adsorbent to the dechlorinating agent is 1:0.25 - 4, preferably 1:0.66 - 1.5. By adopting this preferred embodiment, the regeneration of the adsorbent and the replacement of the dechlorinating agent can be carried out simultaneously, preventing long-term shutdowns caused by multiple replacements or regeneration agents and saving costs.

[0031] According to the present invention, preferably, the bed where the adsorbent is located is a constant temperature zone. By adopting this preferred embodiment, it is beneficial to ensure that the reaction has a high activity.

[0032] According to the present invention, preferably, the temperature of the constant temperature zone is 200 - 450 °C, preferably 380 - 400 °C. By adopting this preferred embodiment, it is beneficial to convert the organic chlorine in the chlorine-containing oil product into inorganic chlorine, thereby improving the dechlorination effect.

[0033] In the present invention, the temperature of the constant temperature zone is the reaction temperature of the reaction in step (1).

[0034] The present invention has no particular limitation on the control means of the temperature, and conventional technical means in the art can be used. The present invention does not make a limitation here.

[0035] The present invention has no particular limitation on the temperature requirement of the bed where the dechlorinating agent is located. The bed where the dechlorinating agent is located can be a constant temperature zone or not. Preferably, the bed where the dechlorinating agent is located is a constant temperature zone.

[0036] According to the present invention, preferably, the reactor is also filled with inert packing, which is placed upstream of the adsorbent and / or downstream of the dechlorinating agent along the direction of the material flow.

[0037] The present invention has a wide selection range for the type of the inert packing, which can be a conventional selection in the art. Ceramic packing is used as an example in the embodiments of the present invention.

[0038] The present invention has a wide selection range for the type of the reactor, and any reactor that can meet the above requirements can be used. Preferably, the reactor is a tubular reactor.

[0039] According to the present invention, preferably, the specific surface area of the adsorbent is 800 - 1000 m 2 / g, preferably 700 - 950 m 2 / g.

[0040] The specific surface area of the adsorbent described in the present invention is measured by the BET method.

[0041] According to the present invention, preferably, the total acidity of the adsorbent is 0.1 - 0.8 mmol / g, preferably 0.4 - 0.7 mmol / g.

[0042] The total acidity of the adsorbent described in the present invention is measured by the Boehm titration method, and the measurement is specifically carried out in accordance with the national standard GB / T 38114 - 2019.

[0043] According to the present invention, preferably, the adsorbent is a modified porous adsorbent, preferably a porous adsorbent modified with oxygen-containing compounds. By adopting this preferred embodiment, the adsorbent is rich in C-H-O active groups, which is beneficial to increasing the reaction rate between organochlorine and the active groups of the adsorbent, and achieving the purpose of quickly converting organochlorine into inorganic chlorine.

[0044] The present invention has a wide selection range for the type of the porous adsorbent, which can be a conventional selection in the art. Preferably, the porous adsorbent is selected from at least one of activated carbon, molecular sieve, and aluminum oxide, preferably activated carbon.

[0045] According to the present invention, preferably, the oxygen-containing compound is nitric acid and / or hydrogen peroxide. For economic and environmental protection considerations, the oxygen-containing compound is preferably hydrogen peroxide.

[0046] According to the present invention, preferably, the molecular sieve is selected from at least one of ZSM-5 molecular sieve, Y-type molecular sieve, and 13X-type molecular sieve.

[0047] According to the present invention, preferably, the preparation method of the adsorbent includes:

[0048] (b-1) Immerse the porous adsorbent in the oxygen-containing compound solution for 12 - 24 h to obtain a suspension;

[0049] (b-2) Dry the suspension obtained in step (b-1).

[0050] According to the present invention, preferably, the volume ratio of the oxygen-containing compound to the porous adsorbent is 5 - 20:1, preferably 6 - 15:1.

[0051] According to the present invention, preferably, the concentration of the oxygen-containing compound is 2 - 30 wt%, preferably 15 - 30 wt%.

[0052] Preferably, the preparation method of the adsorbent further includes: before drying the suspension obtained in step (b-1), first perform solid-liquid separation and washing.

[0053] The present invention does not particularly limit the method of solid-liquid separation, and common technical means in the art can be adopted. The present invention takes suction filtration as an example.

[0054] The present invention does not particularly limit the specific conditions of the washing, and common methods in the art can be adopted as long as the washing reagent used for washing is neutral.

[0055] Preferably, the method for preparing the adsorbent further includes: filtering the washed material.

[0056] The present invention does not particularly limit the conditions of the filtration, and common methods in the art can be adopted. The present invention does not make a limitation here.

[0057] The present invention does not particularly limit the drying conditions, and common methods in the art can be adopted, with the washed material being dried to a constant weight as the criterion. Preferably, the drying conditions include: the temperature is 100-120°C and the time is 2-4h.

[0058] According to the present invention, preferably, the dechlorinating agent includes at least one metal oxide of Group IA, Group IIA, Group VIII, Group IB, and Group IIB of the periodic table and a carrier.

[0059] Preferably, the metal is selected from at least one of Cu, Fe, Zn, and Ca, and preferably Zn and / or Ca. Adopting this preferred embodiment is beneficial to converting inorganic chlorine into stable chlorides.

[0060] The active ingredient of the dechlorinating agent in the present invention is a metal oxide, which basically does not react with organic chlorine at the contact temperature described in the present invention. It is inevitable that the organic chlorine is converted into inorganic chlorine to achieve the dechlorination effect described in this method, and it has a high conversion efficiency.

[0061] The present invention has a wide selection range for the type of the carrier, and various common carriers in the art can be used. The present invention does not make a limitation here. For example, it can be, but is not limited to, one or several of silica, alumina, silica-alumina, and clay.

[0062] According to the present invention, preferably, based on the total weight of the dechlorinating agent, the content of the metal oxide is 50-90% by weight, and preferably 60-80% by weight.

[0063] In the present invention, the balance is the weight of the carrier.

[0064] The present invention does not particularly limit the source of the dechlorinating agent, and it can be obtained through commercial purchase or self-preparation.

[0065] The object of the present invention can be achieved as long as a preparation method capable of preparing a dechlorination agent with the above characteristics is used. The present invention has a wide selection range for the preparation method of the dechlorination agent and can adopt conventional methods in the art. For example, the preparation method of the dechlorination agent includes: mixing a metal oxide with a carrier and forming it, and then drying and calcining.

[0066] The present invention has no particular limitation on the forming, and it can be carried out according to conventional forming methods in the art. For example, it can be, but is not limited to, extrusion forming, spray forming, compression forming, etc. The specific methods are well known to those skilled in the art and will not be elaborated herein.

[0067] The present invention has a wide selection range for the drying conditions and can be carried out with reference to common methods in the art. Preferably, the drying conditions include: a temperature of 100-120°C and a time of 1-4 h.

[0068] The present invention has no particular limitation on the calcination and can be carried out with reference to common methods in the art. Preferably, the calcination conditions include: a temperature of 450-550°C and a time of 3-6 h. The calcination is generally carried out in an air atmosphere, and the air atmosphere can include a flowing atmosphere or a static atmosphere.

[0069] According to the present invention, preferably, the temperature of the reaction is 200-450°C, preferably 380-400°C.

[0070] According to the present invention, preferably, the liquid hourly space velocity of the reaction is 2-20 h -1 , preferably 6-15 h -1 , more preferably 8-12 h -1 .

[0071] According to the present invention, preferably, the contact conditions include: a reaction temperature of 200-450°C, preferably 380-400°C.

[0072] According to the present invention, preferably, the contact conditions include: a contact temperature of 200-450°C, preferably 380-400°C.

[0073] Preferably, the method further includes: feeding the chlorine-containing oil product into the reactor by a pump.

[0074] Preferably, the method further includes: before the reaction in step (1), first introducing a protective gas to exclude air.

[0075] Preferably, the protective gas is selected from at least one of nitrogen, argon, and helium. For economic considerations, the protective gas is preferably nitrogen.

[0076] According to the present invention, preferably, the method further includes: recycling the reacted liquid material as a refinery raw material, and using the non-condensable gas as supplementary fuel gas for auxiliary heating.

[0077] Preferably, the non-condensable gas includes at least one of hydrogen, methane, and carbon dioxide.

[0078] The present invention does not particularly limit the method for the recycling, and conventional technical means in the art can be adopted. Preferably, the present invention adopts the method of cooling and gas-liquid separation for recycling.

[0079] The present invention does not particularly limit the method for the cooling, and it can be carried out with reference to the conventional methods in the art. Preferably, the present invention adopts water cooling and / or air cooling.

[0080] The present invention does not particularly limit the method for the gas-liquid separation, and conventional technical means in the art can be adopted, and the present invention will not elaborate further thereon.

[0081] The method of the present invention is applicable to oils containing different concentrations of organochlorine, especially oils containing high concentrations of organochlorine. Preferably, the content of organochlorine in the oil is 100 - 2000 μg / g.

[0082] According to the present invention, preferably, the distillation range of the oil is IBP - 500 °C, preferably IBP - 350 °C.

[0083] According to the present invention, preferably, the oil is plastic pyrolysis oil, preferably including at least one of gasoline, diesel, and wax oil, and more preferably gasoline and / or diesel.

[0084] When the chlorine content in the dechlorinated oil cannot meet the incoming plant standard for the refining of refinery raw material oil, the adsorbent and dechlorinating agent need to be replaced.

[0085] According to a specific embodiment of the present invention, it will be described in detail in combination with the attached Figure 1 First, the chlorine-containing oil in the raw material storage tank 1 is sent into the reactor 3 through the oil pump 2. Among them, in the order of the material flow direction, the reactor 3 is filled with an inert filler 3.1, an adsorbent 3.2, a dechlorinating agent 3.3, and an inert filler 3.4 in sequence. The chlorine-containing oil reacts with the adsorbent 3.2 to obtain a material W, and then contacts with the dechlorinating agent 3.3. The contacted material is cooled by 4 and then enters the oil-gas separator 5. The separated liquid material (i.e., the dechlorinated oil) enters the dechlorinated oil storage tank 6 for recycling as a refinery raw material, and the non-condensable gas 7 is used as supplementary fuel gas for auxiliary heating.

[0086] According to a specific embodiment of the present invention, the reactor is first subjected to an airtightness test before use.

[0087] The method of the present invention can make the chlorine content in the dechlorinated oil below 30 μg / g, preferably 1-20 μg / g, which can meet the incoming plant standards for the refining of raw oil in existing refineries and broaden the sources of raw oil.

[0088] The chlorine in the dechlorinated oil of the present invention is the unremoved organic chlorine and the unremoved inorganic chlorine obtained by the reaction.

[0089] The present invention will be described in detail below through examples.

[0090] In the following examples, the chlorine content was measured by the light oil chlorine content method (potentiometric titration method). The specific method was as follows: The sample was injected into a quartz cracking tube with a syringe. Under the conditions of high temperature and the presence of oxygen, the chlorine element in the sample was converted into hydrogen chloride gas; the reaction gas was carried into the titration cell by the carrier gas, and the chloride ion reacted with the silver ion in the titration cell as follows: Cl - +Ag + -AgCl. This caused the concentration of silver ions to decrease; the reference-measuring electrode pair indicated this concentration change and transmitted the signal to the amplifier, and the amplifier output a corresponding voltage signal to the electrolytic electrode pair. Silver ions (Ag-Ag + +e) were electrogenerated at the anode to supplement the silver ions consumed by the chloride ions until the chloride ions in the electrolyte returned to the original concentration. The amount of electricity consumed in the whole reaction process was measured, and the chlorine content in the sample could be calculated according to Faraday's electrolysis law.

[0091] The reagents used in the following examples were commercially available products of analytical grade.

[0092] In the following examples and comparative examples, the raw oil used was a mixture of 0# diesel and 1-chlorobutane, with a distillation range of 180-350 °C and a 1-chlorobutane concentration of about 1514 μg / g.

[0093] Preparation Examples I-1 to I-3 were used to illustrate the preparation of the adsorbent

[0094] Preparation Example I-1

[0095] The activated carbon was impregnated in 15 wt% H2O2 for 24 h, and the volume ratio of H2O2 to activated carbon was 10:1 to obtain a suspension. The suspension was filtered by suction, then washed with deionized water until neutral and filtered, and then the filtered material was placed in a blast drying oven at 120 °C and dried for 3 h to obtain the adsorbent. The specific surface area of the adsorbent was 870 m 2 / g, and the total acidity was 0.58 mmol / g.

[0096] Preparation Example I-2

[0097] It was carried out according to the method of Preparation Example I-1, except that 5 wt% H2O2 was used. The specific surface area of the adsorbent was 890 m2 / g, the total acidity is 0.42 mmol / g.

[0098] Preparation Example I-3

[0099] It was carried out according to the method of Preparation Example I-1, except that 30 wt% H2O2 was used. The specific surface area of the adsorbent is 750 m 2 / g, the total acidity is 0.66 mmol / g.

[0100] Example 1

[0101] First, the feedstock oil in the feedstock storage tank 1 was sent into the tubular reactor 3 through the oil pump 2. Among them, in the flow direction of the material, the reactor 3 was filled with inert packing 3.1, adsorbent 3.2, dechlorination agent 3.3 and inert packing 3.4 in sequence. The reactor 3 was first subjected to an airtightness test. After the airtightness was qualified, nitrogen was introduced to remove air. Then the chlorine-containing oil product reacted with the adsorbent 3.2 to obtain the material stream W, and then contacted with the dechlorination agent 3.3. The material W obtained after contact entered the oil-gas separator 5 after cooling 4. The separated liquid material (i.e., dechlorinated oil) entered the dechlorinated oil storage tank 6 for recovery as a refinery feedstock, and the non-condensable gas 7 was used as supplementary fuel gas for auxiliary heating. The beds where the adsorbent and the dechlorination agent are located are both constant temperature zones. The specific parameters in the above process, as well as the residual chlorine amount and dechlorination rate in the dechlorinated oil, are shown in Table 1.

[0102] Example 2

[0103] It was carried out according to the method of Example 1, except that the reaction temperature and the contact temperature were both 375 °C, and the filling volume ratio of the adsorbent to the dechlorination agent was 1.2:1. The residual chlorine amount and dechlorination rate in the obtained dechlorinated oil are shown in Table 1.

[0104] Example 3

[0105] It was carried out according to the method of Example 1, except that the reaction temperature and the contact temperature were both 350 °C, and the filling volume ratio of the adsorbent to the dechlorination agent was 1:1.2. The residual chlorine amount and dechlorination rate in the obtained dechlorinated oil are shown in Table 1.

[0106] Example 4

[0107] It was carried out according to the method of Example 1, except that the LHSV of the feedstock oil was 15 h -1 , and the residual chlorine amount and dechlorination rate in the obtained dechlorinated oil are shown in Table 1.

[0108] Example 5

[0109] It was carried out according to the method of Example 1, except that the adsorbent was I-2, and the filling volume ratio of the adsorbent to the dechlorination agent was 1:1.2. The residual chlorine amount and dechlorination rate in the obtained dechlorinated oil are shown in Table 1.

[0110] Example 6

[0111] It was carried out according to the method of Example 1, except that for Adsorbent I-3, the filling volume ratio of the adsorbent to the dechlorinating agent was 1.2:1. The residual chlorine amount and dechlorination rate in the dechlorinated oil obtained are shown in Table 1.

[0112] Example 7

[0113] It was carried out according to the method of Example 6, except that the dechlorinating agent was II-2. The residual chlorine amount and dechlorination rate in the dechlorinated oil obtained are shown in Table 1.

[0114] Comparative Example 1

[0115] It was carried out according to the method of Example 1, except that Adsorbent I-1 and dechlorinating agent II-1 were not filled, and all were filled with ceramic fillers. The residual chlorine amount and dechlorination rate in the dechlorinated oil obtained are shown in Table 1.

[0116] Comparative Example 2

[0117] It was carried out according to the method of Example 1, except that according to the material flow direction, the dechlorinating agent II-1 was filled in the upper layer and the adsorbent I-1 was filled in the lower layer. The residual chlorine amount and dechlorination rate in the dechlorinated oil obtained are shown in Table 1.

[0118] Table 1

[0119]

[0120]

[0121] Note: For dechlorinating agent II-1, the weight ratio of ZnO, SiO2 and clay is 6:3:1;

[0122] For dechlorinating agent II-2, the weight ratio of CaO, SiO2 and clay is 6:3:1.

[0123] It can be seen from the results in Table 1 that the method of the present invention has significantly better dechlorination effect. It should be noted that the dechlorinating agent containing CaO in Example 7 showed pulverization during actual use, and pipeline blockage occurred after the reactor.

[0124] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for dechlorination of chlorine-containing oil products by reaction, the method comprising: (1) React a chlorine-containing oil product with an adsorbent so that at least part of the organic chlorine in the chlorine-containing oil product is converted into inorganic chlorine to obtain a material W; the specific surface area of the adsorbent is 700-870 m 2 / g; the total acidity of the adsorbent is 0.4-0.7 mmol / g; the total acidity of the adsorbent is measured by the Boehm titration method; (2) contacting material W with a dechlorinating agent to obtain dechlorinated oil; the dechlorinating agent comprises zinc oxide and a carrier; wherein the adsorbent and the dechlorinating agent are filled in different beds of the same reactor, and along the material flow direction, the adsorbent is located upstream of the dechlorinating agent; wherein the temperature of the reaction is 380 - 400 °C; wherein the distillation range of the oil product is IBP - 500 °C; wherein the content of organic chlorine in the oil product is 100 - 2000 μg / g.

2. The method according to claim 1, wherein the filling volume ratio of the adsorbent to the dechlorinating agent is 1:0.25 - 4.

3. The method according to claim 2, wherein the filling volume ratio of the adsorbent to the dechlorinating agent is 1:0.66 - 1.

5.

4. The method according to claim 1, wherein the bed layer where the adsorbent is located is a constant temperature zone.

5. The method according to claim 1, wherein the reactor is further filled with inert packing, which is placed upstream of the adsorbent and / or downstream of the dechlorinating agent along the material flow direction.

6. The method according to claim 1, wherein the reactor is a tubular reactor.

7. The method according to any one of claims 1 - 6, wherein the adsorbent is a modified porous adsorbent material.

8. The method according to claim 7, wherein the adsorbent is a porous adsorbent material modified with an oxygen-containing compound.

9. The method according to claim 8, wherein the porous adsorbent material is selected from at least one of activated carbon, molecular sieve and aluminum oxide.

10. The method according to claim 9, wherein the porous adsorbent material is activated carbon.

11. The method according to claim 8, wherein the oxygen-containing compound is nitric acid and / or hydrogen peroxide.

12. The method according to claim 11, wherein the oxygen-containing compound is hydrogen peroxide.

13. The method according to claim 8, wherein the preparation method of the adsorbent comprises: (b - 1) impregnating the porous adsorbent material in an oxygen-containing compound solution for 12 - 24 h to obtain a suspension; (b - 2) drying the suspension obtained in step (b - 1).

14. The method according to claim 13, wherein the volume ratio of the oxygen-containing compound to the porous adsorbent material is 5 - 20:

1.

15. The method according to claim 14, wherein the volume ratio of the oxygen-containing compound to the porous adsorbent material is 6 - 15:

1.

16. The method according to claim 13, wherein the concentration of the oxygen-containing compound is 2 - 30 wt%.

17. The method according to claim 16, wherein the concentration of the oxygen-containing compound is 15 - 30 wt%.

18. The method according to any one of claims 1 - 6, wherein based on the total weight of the dechlorinating agent, the content of metal oxide is 50 - 90% by weight.

19. The method according to claim 18, wherein based on the total weight of the dechlorinating agent, the content of metal oxide is 60 - 80% by weight.

20. The method according to any one of claims 1-6, wherein, The liquid hourly space velocity of the reaction is 2 - 20 h -1 .

21. The method according to claim 20, wherein, The liquid hourly space velocity of the reaction is 6-15 h -1 .

22. The method according to claim 21, wherein, The liquid hourly space velocity of the reaction is 8 - 12 h -1 .

23. The method according to any one of claims 1-6, wherein, the conditions of the contact include: the reaction temperature is 200-450 °C.

24. The method according to claim 23, wherein, the conditions of the contact include: the reaction temperature is 380-400 °C.

25. The method according to any one of claims 1-6, wherein, the distillation range of the oil product is IBP-350 °C.

26. The method according to any one of claims 1-6, wherein, the oil product is pyrolysis oil of plastics.

27. The method according to claim 26, wherein, the oil product includes at least one of gasoline, diesel oil and wax oil.

28. The method according to claim 27, wherein, the oil product is gasoline and / or diesel oil.

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