An olefin removal reaction of reformate, and a reaction device and method for chlorine removal and olefin removal

Abstract

The present disclosure relates to a de-olefination reaction of reformate and a reaction apparatus and method for de-chlorination and de-olefination. The de-olefination reaction includes contacting reformate with a de-olefination catalyst for reaction. The de-olefination catalyst includes a sulfate-containing alumina support and active components. The active components include elemental Pd, elemental Pt, and chloride ions. Based on the total weight of alumina, the content of elemental Pd is 0.1-0.2 wt%, the content of elemental Pt is 0.01-0.15 wt%, the content of chloride ions is 0.4-2.0 wt%, and the content of sulfate is 0.4-2.0 wt%. The temperature of the contacting reaction is 35-80 °C. The method of the present disclosure performs de-chlorination and de-olefination of reformate in the same reactor, fully utilizes the dissolved hydrogen in reformate, removes chlorine and some olefins in reformate with a relatively high reaction efficiency, and can extend the service life of the subsequent tandem clay. The process is simple and flexible, and occupies a small area.

Description

Technical Field

[0001] The present disclosure relates to the field of reformate treatment, and in particular, to a de-olefination reaction of reformate, and a reaction device and method for de-chlorination and de-olefination. Background Art

[0002] During the reforming reaction process, a part of the chlorine combined on the reforming catalyst enters the reformate, which will cause a series of problems such as ammonium salt blockage, chloride corrosion, and deterioration of extraction solvent in downstream equipment. Therefore, before the reformate enters the de-pentane tower, a reforming liquid-phase de-chlorination tank is set up to remove trace chlorides in the reformate. The reformate contains a certain amount of unsaturated olefins, which seriously affect the stable operation and product quality of subsequent units such as aromatics extraction. Therefore, the reformate usually needs to be pretreated before entering downstream units such as aromatics extraction.

[0003] Conventionally, the method of clay refining is used to remove olefins in the reformate. Due to the relatively low specific surface area and weak acidity of the clay, it is easy to be adsorbed and saturated, so its service life is short and it needs to be replaced frequently, increasing the workload of the operator. In addition, the clay cannot be regenerated after inactivation, and a large amount of waste clay needs to be landfilled or specially treated as hazardous waste, which is not conducive to environmental protection. The method of molecular sieve catalytic refining refers to a technology for removing trace olefins in reformate by using catalysts containing molecular sieves such as X, Y, β, SAPO-34, and MCM-22 under non-hydrogenation reaction conditions. Although the service life of the de-olefination catalyst containing molecular sieve is longer than that of clay, its single-pass life is still relatively short, and it still needs to be unloaded for out-of-reactor regeneration after inactivation. Waste clay and the finally inactivated molecular sieve-containing catalyst need to be landfilled or specially treated as hazardous waste, which is not conducive to environmental protection. In addition, both clay and molecular sieve-containing catalysts remove olefins by alkylation, polymerization, and condensation reactions, resulting in an increase in the dry point of the reaction product and the content of heavy aromatics.

[0004] Selective hydrogenation refers to selective hydrogenation and de-olefination of reformate and raffinate under hydrogenation conditions to achieve deep hydrogenation and removal of olefins therein without hydrogenating and saturating aromatics. The catalysts used mainly contain non-noble metal (such as Co-Mo or Ni-Mo) and noble metal (including Pt, Pd, etc.) catalysts. The latter is expensive and has a good effect on removing olefins in benzene, but for aromatic products with a wide boiling range from benzene to xylene, it is difficult to comprehensively balance the hydrogenation reaction depth, and the loss of aromatics is relatively significant. In addition, due to the relatively high reaction pressure and temperature, a new hydrogenation unit needs to be built, with a high investment. Summary of the Invention

[0005] The object of the present disclosure is to provide a de-olefination reaction of reformate and a reaction apparatus and method for de-chlorination and de-olefination, which can remove chlorine and some olefins in reformate with a relatively high reaction efficiency and has a small floor area of the apparatus.

[0006] To achieve the above object, in a first aspect of the present disclosure, a de-olefination reaction of reformate is provided, and the de-olefination reaction includes: contacting reformate with a de-olefination catalyst for reaction;

[0007] The de-olefination catalyst includes an alumina support containing sulfate and an active component, and the active component includes elemental Pd, elemental Pt, and chloride ions;

[0008] Based on the total weight of alumina, the content of elemental Pd is 0.1-0.2% by weight, the content of elemental Pt is 0.01-0.15% by weight, the content of chloride ions is 0.4-2.0% by weight, and the content of sulfate is 0.4-2.0% by weight;

[0009] The temperature of the contacting reaction is 35-80 °C.

[0010] Optionally, based on the total weight of alumina, the content of sodium element is 0-0.05% by weight.

[0011] Optionally, the specific surface area of the alumina support containing sulfate is 180-300 m 2 / g, the total pore volume is 0.50-1.20 cm 3 / g, and the average particle size is 1.2-1.8 mm;

[0012] Preferably, the alumina support containing sulfate is a γ-Al2O3 support containing sulfate;

[0013] The specific surface area of the de-olefination catalyst is 180-300 m 2 / g, the total pore volume is 0.50-1.20 cm 3 / g, and the average particle size is 1.2-1.8 mm.

[0014] Optionally, the pressure of the contacting reaction is 2.0-3.0 MPa, and the weight hourly space velocity of the reformate to the de-olefination catalyst is 15-25 h -1 ; the contacting reaction is carried out under non-hydrogenation conditions.

[0015] Optionally, the reformate is a full-range reformate containing dissolved hydrogen, the chlorine content of the reformate is 2-4 mg / Kg, and the bromine index is 2000-5000 mgBr / 100 g.

[0016] The second aspect of the present disclosure provides a reaction device for dechlorination and deolefination of reformed product oil. The reaction device includes a first reactor, and the first reactor includes a dechlorination treatment zone and a deolefination treatment zone;

[0017] A dechlorinating agent is filled in the dechlorination treatment zone, and a deolefination catalyst is filled in the deolefination treatment zone;

[0018] The deolefination catalyst includes a sulfate-containing alumina carrier and an active component, and the active component includes elemental Pd, elemental Pt and chloride ions;

[0019] Based on the total weight of alumina, the content of elemental Pd is 0.1-0.2% by weight, the content of elemental Pt is 0.01-0.15% by weight, the content of chloride ions is 0.4-2.0% by weight, and the content of sulfate is 0.4-2.0% by weight.

[0020] Optionally, the dechlorinating agent is in the shape of a cylindrical bar, with a diameter of 1.5-3.5 mm, a length of 5-15 mm, a bulk specific gravity of 0.60-0.80 g / mL, a crush strength ≥ 30 N / cm, and a breakthrough chlorine capacity ≥ 16%;

[0021] The dechlorinating agent includes calcium oxide, zinc oxide and alumina;

[0022] Relative to the total weight of the dechlorinating agent, the content of calcium oxide is 50-60% by weight, the content of zinc oxide is 2-10% by weight, and the content of alumina is 30-40% by weight;

[0023] Optionally, the volume ratio of the dechlorinating agent to the deolefination catalyst is (1.5-2.5):1.

[0024] Optionally, based on the total weight of alumina, the content of sodium element is 0-0.05% by weight;

[0025] Optionally, the specific surface area of the sulfate-containing alumina carrier is 180-300 m 2 / g, the total pore volume is 0.50-1.20 cm 3 / g, and the average particle size is 1.2-1.8 mm;

[0026] Preferably, the sulfate-containing alumina carrier is a sulfate-containing γ-Al2O3 carrier;

[0027] The specific surface area of the deolefination catalyst is 180-300 m 2 / g, the total pore volume is 0.50-1.20 cm 3 / g, and the average particle size is 1.2-1.8 mm.

[0028] Optionally, a reformate inlet is provided at the upper end of the reactor, and a first treated oil outlet is provided at the lower end of the first reactor;

[0029] The deolefination treatment zone is closer to the reformate inlet than the dechlorination treatment zone.

[0030] Optionally, the reaction device further includes a second reactor, a recontacting device, and a stabilizer;

[0031] The second reactor is filled with clay;

[0032] The reformate outlet of the recontacting device is connected to the reformate inlet;

[0033] The first treated oil inlet of the stabilizer is connected to the first treated oil outlet;

[0034] The second treated oil inlet of the second reactor is connected to the second treated oil outlet of the stabilizer.

[0035] A third aspect of the present disclosure provides a method for dechlorinating and deolefining reformate, the method including: introducing reformate into the first reactor described in the second aspect of the present disclosure, and contacting and reacting with the dechlorinating agent and the deolefination catalyst.

[0036] Optionally, the operating pressure of the first reactor is 2.0 - 3.0 MPa, the operating temperature is 35 - 80 °C, the weight hourly space velocity of the reformate with respect to the dechlorinating agent is 5 - 10 h -1 , and the weight hourly space velocity of the reformate with respect to the deolefination catalyst is 15 - 25 h -1 ; the contacting reaction is carried out under non-hydrogen conditions.

[0037] Optionally, the reformate is a full-range reformate output from the recontacting device and containing dissolved hydrogen, the chlorine content of the reformate is 2 - 4 mg / Kg, and the bromine index is 2000 - 5000 mgBr / 100 g.

[0038] Through the above technical solutions, the deolefination catalyst of the present disclosure uses alumina containing sulfate as a carrier, and loads specific contents of elemental Pd, elemental Pt, and chloride ions as active components, and can achieve the deolefination reaction of reformate at a lower temperature. The method of the present disclosure performs dechlorination and deolefination of reformate in the same reactor, fully utilizes the dissolved hydrogen in the reformate, removes chlorine and some olefins in the reformate with a high reaction efficiency, greatly reduces the consumption of clay and the emission of hazardous waste, reduces the operation risk of loading and unloading clay in the device, and can extend the service life of the subsequent series-connected clay. The process is simple and flexible, can be achieved only by making minor modifications on the basis of the existing device, and occupies a small area.

[0039] Other features and advantages of the present disclosure will be described in detail in the following detailed description section. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The accompanying drawings are used to provide a further understanding of the present disclosure, and constitute a part of the specification. Together with the following detailed description, they are used to explain the present disclosure, but do not constitute a limitation to the present disclosure. In the drawings:

[0041] Figure 1 is a schematic structural diagram of the first reactor of Embodiment 1 of the present disclosure.

[0042] DESCRIPTION OF REFERENCE NUMERALS

[0043] 1. Reformed product oil inlet 13. φ3 ceramic balls

[0044] 2. Reactor manhole 14. Deolefinization catalyst

[0045] 3. First treated oil outlet 15. φ3 ceramic balls

[0046] 11. φ19 ceramic balls 16. Dechlorination agent

[0047] 12. φ6 ceramic balls 17. φ19 ceramic balls DETAILED DESCRIPTION

[0048] The following detailed description of the present disclosure will be made with reference to the accompanying drawings. It should be understood that the detailed description herein is only for the purpose of illustration and explanation of the present disclosure, and is not intended to limit the present disclosure.

[0049] The first aspect of the present disclosure provides a deolefinization reaction of reformed product oil, and the deolefinization reaction includes: contacting and reacting the reformed product oil with a deolefinization catalyst;

[0050] The deolefinization catalyst includes an alumina support containing sulfate and an active component, and the active component includes elemental Pd, elemental Pt, and chloride ions;

[0051] Based on the total weight of alumina, the content of elemental Pd is 0.1 - 0.2% by weight, the content of elemental Pt is 0.01 - 0.15% by weight, the content of chloride ions is 0.4 - 2.0% by weight, and the content of sulfate is 0.4 - 2.0% by weight;

[0052] The temperature of the contacting reaction is 35 - 80 °C.

[0053] According to an embodiment of the present disclosure, based on the total weight of alumina, the content of elemental Pd is 0.15-0.2 wt%, the content of elemental Pt is 0.07-0.15 wt%, the content of chloride ions is 0.8-1.2 wt%, and the content of sulfate radicals is 0.5-1.5 wt%.

[0054] The de-olefin catalyst of the present disclosure uses alumina containing sulfate radicals as a carrier and loads specific contents of elemental Pd, elemental Pt, and chloride ions as active components, which can achieve the de-olefin treatment of reformed naphtha at a lower temperature and can extend the service life of the subsequent tandem clay.

[0055] In the present disclosure, the sulfate radicals exist in the form of sulfates.

[0056] According to an embodiment of the present disclosure, based on the total weight of alumina, the content of sodium element is 0-0.05 wt%.

[0057] According to an embodiment of the present disclosure, the specific surface area of the alumina carrier containing sulfate radicals is 180-300 m 2 / g, preferably 185-280 m 2 / g; the total pore volume is 0.50-1.20 cm 3 / g, preferably 0.55-1.00 cm 3 / g; the average particle size is 1.2-1.8 mm, preferably 1.4-1.8 mm; further preferably, the alumina carrier containing sulfate radicals is a γ-Al2O3 carrier containing sulfate radicals.

[0058] According to an embodiment of the present disclosure, the specific surface area of the de-olefin catalyst is 180-300 m 2 / g, preferably 185-280 m 2 / g; the total pore volume is 0.50-1.20 cm 3 / g, preferably 0.55-1.00 cm 3 / g; the average particle size is 1.2-1.8 mm, preferably 1.4-1.8 mm.

[0059] According to an embodiment of the present disclosure, the de-olefin catalyst of the present disclosure can be prepared by the following steps:

[0060] (1) Preparation of the alumina precursor containing sulfate radicals

[0061] The alumina precursor containing sulfate radicals is preferably boehmite containing sulfate radicals, and the preparation steps are as follows:

[0062] Add an aluminum sulfate solution to a sodium metaaluminate solution, adjust the pH value of the solution to 7.0 - 7.5, and stir and react at 30 - 70 °C for 30 - 60 min; then add a sodium carbonate solution to adjust the pH value of the solution to 8.0 - 9.0, and continue to stir and react for 30 - 60 min; subject the obtained mixed solution to an aging treatment, wash the obtained solid with water until the sulfate content is within the sulfate content range of the olefin - removing catalyst of the present disclosure, and then perform a drying treatment;

[0063] The conditions for the aging treatment include: a time of 7 - 24 h and a temperature of 40 - 95 °C;

[0064] The conditions for the drying treatment include: a time of 12 - 24 h and a temperature of 100 - 150 °C;

[0065] (2) Preparation of a sulfate - containing alumina support

[0066] Mix sulfate - containing pseudoboehmite, an extrusion aid, a peptizing agent, and water, knead them evenly, extrude them into shapes, and then perform a drying treatment and a calcination treatment; the mass ratio of sulfate - containing pseudoboehmite, extrusion aid, peptizing agent, and water is 50:(1 - 1.5):(5 - 8):(35 - 45);

[0067] Among them, the extrusion aid includes, but is not limited to, powdered sesbania, and the peptizing agent can be selected from any one, any two, or any three of nitric acid, acetic acid, and citric acid;

[0068] The conditions for the drying treatment include: a temperature of 100 - 130 °C and a time of 6 - 20 h;

[0069] The conditions for the calcination treatment include: a temperature of 500 - 700 °C and a time of 2 - 10 h;

[0070] Preferably, treat the sulfate - containing alumina support dried and calcined with steam at 400 - 700 °C for 0.5 - 120 h; the specific treatment method includes: introducing saturated or supersaturated steam at 60 - 150 °C into the processor, and the mass ratio of the steam used in the steam treatment to the sulfate - containing alumina support is (0.2 - 10):1, preferably (0.3 - 5):1;

[0071] (3) Loading of active components

[0072] Add a sulfate - containing alumina support to an impregnation solution containing a platinum source, a palladium source, and a chlorine source, perform an impregnation treatment, and subject the obtained solid to a drying treatment, a calcination treatment, and a hydrogen reduction treatment;

[0073] Among them, the platinum source is selected from one or more of chloroplatinic acid, dichlorotetraammineplatinum, ammonium chloroplatinate, platinum trichloride, and platinum tetrachloride, preferably chloroplatinic acid; the palladium source is selected from one or more of palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, and dichlorotetraamminepalladium, preferably palladium chloride; the chlorine source can be a chlorine-containing organic acid and / or a chlorine-containing inorganic acid, preferably hydrochloric acid. The content of platinum element in the impregnating solution is 0.01 - 0.15 wt%, the content of palladium element is 0.1 - 0.2 wt%, and the content of chlorine element is 0.4 - 2.0 wt%.

[0074] The impregnation treatment can be carried out in a rotary vacuum evaporator. The specific operation method is: carry out the impregnation treatment under the conditions of 0.001 - 0.10 MPa and rotation. The volume ratio of the impregnating solution to the sulfate group-containing alumina support is (1.1 - 3.0):1, the linear velocity of rotation is 0.01 - 2.0 m / s, and the solid obtained after impregnation is subjected to drying treatment, calcination treatment in dry air, and hydrogen reduction treatment. The pressure of vacuum rotary impregnation is preferably 0.001 - 0.08 MPa. During impregnation, heat and rotate simultaneously. The heating temperature, i.e., the impregnation temperature, is preferably 20 - 90 °C. The rotation rate should not be too fast, and the preferred linear velocity of rotation is 0.02 - 0.8 m / s. The impregnation time is preferably 1 - 8 h, more preferably 2 - 4 h. After vacuum rotary impregnation, the water in the impregnating solution has basically evaporated, and the catalyst pre-product is in a dry state. At this time, it can be directly taken out for drying treatment, calcination treatment in dry air, and hydrogen reduction treatment;

[0075] The conditions of the drying treatment include: the temperature is 100 - 180 °C, and the time is 8 - 16 h;

[0076] The conditions of the calcination treatment include: the temperature is 400 - 650 °C, the time is 4 - 8 h, and the gas / catalyst volume ratio is (400 - 900):1;

[0077] The conditions of the hydrogen reduction treatment include: the temperature is 350 - 550 °C, the time is 4 - 8 h, and the gas / catalyst volume ratio is (300 - 800):1.

[0078] According to an embodiment of the present disclosure, the temperature of the contact reaction is 35 - 45 °C.

[0079] According to an embodiment of the present disclosure, the pressure of the contact reaction is 2.0 - 3.0 MPa, preferably 2.2 - 2.8 MPa; the weight hourly space velocity of the reformate oil to the de-olefin catalyst is 15 - 25 h -1 , preferably 17 - 22 h -1 ; the contact reaction is carried out under non-hydrogen conditions, preferably in an inert atmosphere. The inert atmosphere includes one or more of a nitrogen atmosphere, a helium atmosphere, and an argon atmosphere.

[0080] According to an embodiment of the present disclosure, the reformate is a full-range reformate containing dissolved hydrogen, the chlorine content of the reformate is 2 - 4 mg / Kg, and the bromine index is 2000 - 5000 mgBr / 100 g.

[0081] The second aspect of the present disclosure provides a reaction device for dechlorination and de-olefination of reformate. The reaction device includes a first reactor, and the first reactor includes a dechlorination treatment zone and a de-olefination treatment zone;

[0082] A dechlorinating agent is loaded in the dechlorination treatment zone, and a de-olefination catalyst is loaded in the de-olefination treatment zone;

[0083] The de-olefination catalyst includes an alumina support containing sulfate and an active component. The active component includes elemental Pd, elemental Pt, and chloride ions;

[0084] Based on the total weight of alumina, the content of elemental Pd is 0.1 - 0.2 wt%, the content of elemental Pt is 0.01 - 0.15 wt%, the content of chloride ions is 0.4 - 2.0 wt%, and the content of sulfate is 0.4 - 2.0 wt%.

[0085] According to an embodiment of the present disclosure, based on the total weight of alumina, the content of elemental Pd is 0.15 - 0.2 wt%, the content of elemental Pt is 0.07 - 0.15 wt%, the content of chloride ions is 0.8 - 1.2 wt%, and the content of sulfate is 0.5 - 1.5 wt%.

[0086] In the present disclosure, the de-olefination treatment zone and the dechlorination treatment zone in the first reactor are arranged at intervals. For example, ceramic balls can be arranged between the de-olefination treatment zone and the dechlorination treatment zone.

[0087] According to an embodiment of the present disclosure, the dechlorinating agent is in the shape of a cylindrical bar, with a diameter of 1.5 - 3.5 mm, a length of 5 - 15 mm, a bulk ratio of 0.60 - 0.80 g / mL, a crushing strength ≥ 30 N / cm, and a breakthrough chlorine capacity ≥ 16%; the dechlorinating agent includes calcium oxide, zinc oxide, and alumina; based on the total weight of the dechlorinating agent, the content of calcium oxide is 50 - 60 wt%, the content of zinc oxide is 2 - 10 wt%, and the content of alumina is 30 - 40 wt%.

[0088] According to an embodiment of the present disclosure, the volume ratio of the dechlorinating agent to the de-olefination catalyst is (1.5 - 2.5):1, preferably (1.6 - 2.2):1. The above volume ratio refers to the loading volume of the dechlorinating agent and the de-olefination catalyst, which is obtained by multiplying the loading height by the effective cross-sectional area of the reactor.

[0089] According to an embodiment of the present disclosure, based on the total weight of alumina, the content of sodium element is 0 - 0.05 wt%.

[0090] According to an embodiment of the present disclosure, the specific surface area of the alumina support containing sulfate is 180 - 300 m 2 / g, preferably 185 - 280 m 2 / g; the total pore volume is 0.50 - 1.20 cm 3 / g, preferably 0.55 - 1.00 cm 3 / g; the average particle size is 1.2 - 1.8 mm, preferably 1.4 - 1.8 mm; further preferably, the alumina support containing sulfate is a γ - Al2O3 support containing sulfate.

[0091] According to an embodiment of the present disclosure, the specific surface area of the de - olefin catalyst is 180 - 300 m 2 / g, preferably 185 - 280 m 2 / g; the total pore volume is 0.50 - 1.20 cm 3 / g, preferably 0.55 - 1.00 cm 3 / g; the average particle size is 1.2 - 1.8 mm, preferably 1.4 - 1.8 mm.

[0092] According to an embodiment of the present disclosure, a reformate inlet is provided at the upper end of the first reactor, and a first treated oil outlet is provided at the lower end of the first reactor; the de - olefin treatment zone is closer to the reformate inlet than the de - chlorination treatment zone, that is, the first reactor is successively the reformate inlet, the de - olefin treatment zone, the de - chlorination treatment zone, and the first treated oil outlet from top to bottom; ceramic balls are provided between the de - olefin treatment zone and the de - chlorination treatment zone, for example, φ3 ceramic balls can be used; in a specific embodiment, the first reactor is successively filled with φ19 ceramic balls, φ6 ceramic balls, φ3 ceramic balls, de - olefin catalyst, φ3 ceramic balls, de - chlorinating agent, and φ19 ceramic balls from bottom to top; in another specific embodiment, the first reactor is successively filled with φ19 ceramic balls, φ6 ceramic balls, φ3 ceramic balls, de - chlorinating agent, φ3 ceramic balls, de - olefin catalyst, and φ19 ceramic balls from bottom to top; adopting the above filling method can play the roles of de - chlorination and de - olefination, and the ceramic balls can physically separate the de - olefin catalyst and the de - chlorinating agent.

[0093] According to an embodiment of the present disclosure, the reaction device further includes a second reactor, a re - contact device, and a stabilizer; the second reactor is filled with clay; the reformate outlet of the re - contact device is connected to the reformate inlet; the first treated oil inlet of the stabilizer is connected to the first treated oil outlet; the second treated oil inlet of the second reactor is connected to the second treated oil outlet of the stabilizer. Among them, the re - contact device and the stabilizer are conventional in the art and will not be elaborated here.

[0094] The third aspect of the present disclosure provides a method for dechlorination and deolefination of reformate, which includes: introducing reformate into the first reactor described in the second aspect of the present disclosure to contact and react with the dechlorinating agent and the deolefination catalyst.

[0095] In the present disclosure, the contact reaction between reformate and the dechlorinating agent and the contact reaction between reformate and the deolefination catalyst are carried out separately in the first reactor. That is, reformate undergoes a contact reaction with the deolefination catalyst in the deolefination treatment zone and a contact reaction with the dechlorinating agent in the dechlorination treatment zone.

[0096] According to an embodiment of the present disclosure, the operating pressure of the first reactor is 2.0 - 3.0 MPa, preferably 2.2 - 2.8 MPa; the operating temperature is 35 - 80 °C, preferably 35 - 45 °C; the weight hourly space velocity of reformate with respect to the dechlorinating agent is 5 - 10 h -1 , preferably 6 - 9 h -1 ; the weight hourly space velocity of reformate with respect to the deolefination catalyst is 15 - 25 h -1 , preferably 17 - 22 h -1 ; the contact reaction is carried out under non-hydrogen conditions, preferably under an inert atmosphere, and the inert atmosphere includes one or more of a nitrogen atmosphere, a helium atmosphere, and an argon atmosphere.

[0097] According to an embodiment of the present disclosure, the reformate is a full-range reformate output from a re-contact device and containing dissolved hydrogen, the chlorine content of the reformate is 2 - 4 mg / Kg, and the bromine index is 2000 - 5000 mgBr / 100 g.

[0098] In the present disclosure, the processes of dechlorination and deolefination of reformate are carried out in the same reactor, reducing the floor area of the device; high reaction efficiency can be obtained at a relatively low temperature, and the dissolved hydrogen in the feedstock oil can be fully utilized.

[0099] The following further illustrates the present disclosure through examples, but the present disclosure is not limited thereby. The raw materials used in the following examples and comparative examples are all commercially available unless otherwise specified.

[0100] Test method and instrument model for specific surface area: The specific surface area of the catalyst is determined by the BET method, and the test instrument is the ASAP2400 static nitrogen adsorption instrument of Micromerities Company, USA.

[0101] Test method and instrument model for average particle size: The particle sizes of the catalyst and the carrier are manually measured using a ruler, and the average value is taken after measuring the particle sizes of 20 catalysts or carriers.

[0102] Testing method and instrument model for total pore volume: The total pore volume of the catalyst was determined by the BET method, and the testing instrument was an ASAP2400 static nitrogen adsorption instrument produced by Micromerities, USA.

[0103] The testing methods and instrument models for the contents of sulfate radical, elemental Pd, elemental Pt, chloride ion, and sodium element in the catalyst are as follows:

[0104] The content of sulfate radical was determined by infrared spectroscopy and analyzed on a CS-34 infrared sulfur and carbon analyzer produced by LECO Corporation, USA;

[0105] The contents of elemental Pd and elemental Pt were determined by X-ray fluorescence spectroscopy and analyzed on a Rigaku 3271E X-ray fluorescence spectrometer made in Japan;

[0106] The content of chloride ion was determined by the ion selective electrode method and analyzed on a 410P-58c chloride ion concentration measuring instrument;

[0107] The content of sodium element was determined by atomic absorption method and analyzed on a novAA300 atomic absorption spectrometer.

[0108] Testing method and instrument model for bromine index: The bromine index was determined by the coulometric method and analyzed on a TBR-2000 bromine value and bromine index measuring instrument produced by Jiangsu Shengtuo Precision Instruments Co., Ltd.

[0109] Testing method and instrument model for chlorine content: The chlorine content was determined by X-ray fluorescence method and measured on a Rigaku 3271E X-ray fluorescence spectrometer made in Japan.

[0110] Olefin removal rate = 100% × (raw material bromine index - product bromine index) / raw material bromine index.

[0111] In the following examples and comparative examples, the second reactor filled with clay had an operating pressure of 1.0 MPa, an operating temperature of 150 °C, and a weight hourly space velocity of 2 h -1 The service life of the clay refers to the time from the start of use to complete inactivation of the clay.

[0112] Example 1

[0113] (1) Preparation of sulfate-containing pseudo-boehmite powder

[0114] Take 500 mL of sodium aluminate solution with a concentration of 210 g / mL, add a certain amount of aluminum sulfate solution with a concentration of 55 g / mL, adjust the pH value of the slurry to 7.3, heat to 65 °C, stir well, and react for 60 min; then add sodium carbonate solution to adjust the pH value of the system to 8.4, continue to stir and react for 60 min, and age at 90 °C for 7 h. Wash the filtered cake with deionized water at 90 °C, with 500 mL of water used each time, and wash 10 times in total. Dry the cake obtained from the last wash at 120 °C for 12 h to obtain pseudo-boehmite powder containing sulfate.

[0115] (2) Preparation of alumina support containing sulfate

[0116] Take the pseudo-boehmite powder containing sulfate prepared in step (1), mix and knead evenly according to the mass ratio of pseudo-boehmite powder: sesbania powder: nitric acid: acetic acid: citric acid: water = 50:1:2:3:3:40, then extrude into strips, dry the wet strips at 120 °C for 12 h, calcine at 650 °C for 4 h, and then pass saturated water vapor at 100 °C (saturated vapor pressure 0.1 MPa) to treat at 650 °C for 4 h. The volume ratio of the air containing water vapor to the support is 700:1, and the mass ratio of water vapor to the support is 0.7:1 to obtain the γ-Al2O3 support ZT-1 containing sulfate.

[0117] (3) Loading of active components

[0118] Take the γ-Al2O3 support containing sulfate prepared in step (2), prepare an impregnation solution with chloroplatinic acid, palladium chloride and hydrochloric acid, so that the impregnation solution contains 0.05 wt% of Pt element, 0.18 wt% of Pd element and 1.0 wt% of Cl element (relative to the mass of dry-based alumina), the pH value of the impregnation solution is 5, and the volume ratio of the impregnation solution to the support is 1.5:1. Pour the support and the impregnation solution into a 500 mL flask, impregnate and treat at 30 °C, 0.08 MPa and a rotational linear speed of 0.03 m / s on a rotary vacuum evaporator for 3 h, evacuate at 70 °C to make the solid in a flowing dry state, unload and dry at 120 °C for 12 h, calcine in dry air at 500 °C under the condition of a gas / catalyst volume ratio of 700:1 for 4 h, and then reduce with H2 at 480 °C under the condition of a gas / catalyst volume ratio of 500:1 for 4 h to obtain the de-olefin catalyst A1. The parameters of the support and the catalyst are listed in Table 1.

[0119] (4) Adopt Figure 1 the filling method, and fill the first reactor from bottom to top with φ19 porcelain balls 11, φ6 porcelain balls 12, φ3 porcelain balls 13, de-olefin catalyst 14, φ3 porcelain balls 15, dechlorination agent 16 (produced by Jinan Ruidong Industry Co., Ltd., brand RDL-100) and φ19 porcelain balls 17 in sequence. The volume ratio of the dechlorination agent to the de-olefin catalyst is 2:1.

[0120] The deolefinization catalyst 14 is the deolefinization catalyst A1 prepared in step (3); the diameter of the dechlorination agent 16 is 2.5 mm, the length is 10 mm, the bulk ratio is 0.75 g / mL, the crushing strength is 50 N / cm, and the breakthrough chlorine capacity is 25%; the dechlorination agent comprises 60% by weight of calcium oxide, 2.5% by weight of zinc oxide and 37.5% by weight of alumina.

[0121] Reaction process conditions: temperature 40°C, pressure 2.0 MPa, nitrogen atmosphere, the weight hourly space velocity of the reformate to the deolefinization catalyst A1 is 18.5 h -1 and the weight hourly space velocity of the reformate to the dechlorination agent is 7.5 h -1 .

[0122] The composition of the reformate raw material is shown in Table 2, the bromine index is 3537 mgBr / 100 g, and the chlorine content is 2.5 mg / kg. The composition of the product is shown in Table 3, the bromine index is 2502 mgBr / 100 g, the chlorine content is 0.5 mg / kg, the olefin removal rate is 29.3%, and the service life of the subsequent series-connected clay is 12 months.

[0123] Example 2

[0124] The method of Example 1, the deolefinization catalyst A1 and the dechlorination agent are used for the dechlorination and deolefinization treatment of the reformate. In the first reactor, φ19 ceramic balls, φ6 ceramic balls, φ3 ceramic balls, the dechlorination agent, φ3 ceramic balls, the deolefinization catalyst and φ19 ceramic balls are loaded in sequence from bottom to top. The chlorine content of the product is 0.5 mg / kg, the bromine index of the product is 2561 mgBr / 100 g, the olefin removal rate is 27.6%, and the service life of the subsequent series-connected clay is 11 months.

[0125] Example 3

[0126] The deolefinization catalyst A2 is prepared by the method of Example 2 and used for the dechlorination and deolefinization treatment of the reformate. The difference is that the deolefinization catalyst A1 is replaced with an equal volume of catalyst A2. The reaction process conditions: temperature 40°C, pressure 2.0 MPa, nitrogen atmosphere, the weight hourly space velocity of the reformate to the deolefinization catalyst A2 is 18.5 h -1 and the weight hourly space velocity of the reformate to the dechlorination agent is 7.5 h -1 . The parameters of the deolefinization catalyst A2 are listed in Table 1.

[0127] The chlorine content of the product is 0.5 mg / kg, the bromine index of the product is 2630 mgBr / 100 g, the olefin removal rate is 25.6%, and the service life of the subsequent series-connected clay is 10 months.

[0128] Example 4

[0129] The deolefinization catalyst A3 was prepared by the method of Example 2, and the reformate was subjected to dechlorination and deolefinization treatment. The difference was that the deolefinization catalyst A1 was replaced with an equal volume of catalyst A3. The reaction process conditions were: temperature 50°C, pressure 2.2 MPa, nitrogen atmosphere, and the weight hourly space velocity of the reformate over the deolefinization catalyst A3 was 15.8 h -1 , and the weight hourly space velocity of the reformate over the dechlorination agent was 7.5 h -1 .

[0130] The chlorine content of the product was 0.5 mg / kg, the bromine index of the product was 2710 mgBr / 100 g, the olefin removal rate was 23.4%, and the service life of the subsequent tandem clay was 9 months.

[0131] Comparative Example 1

[0132] The reformate was subjected to dechlorination and deolefinization treatment by the method of Example 1. The difference was that there was only a dechlorination agent in the reactor and no deolefinization catalyst.

[0133] The chlorine content of the product was 0.5 mg / kg, the bromine index of the product was 3530 mgBr / 100 g, the olefin removal rate was 0.2%, and the service life of the subsequent tandem clay was 6 months.

[0134] Comparative Example 2

[0135] The reformate was subjected to dechlorination and deolefinization treatment by the method of Example 2. The difference was that the deolefinization catalyst A1 was replaced with an equal volume of molecular sieve catalyst (developed by the Research Institute of Petroleum Processing, SINOPEC, produced by Shenzhen Mingquansheng Catalyst Co., Ltd., grade TOR-1).

[0136] The chlorine content of the product was 0.5 mg / kg, the bromine index of the product was 3460 mgBr / 100 g, the olefin removal rate was 2.2%, and the service life of the subsequent tandem clay was 7 months.

[0137] Comparative Example 3

[0138] The reformate was subjected to dechlorination and deolefinization treatment by the method of Example 2. The difference was that the deolefinization catalyst A1 was replaced with an equal volume of modified clay (produced by Jiangxi Anji Zhongxin Activated Clay Co., Ltd., grade ROC).

[0139] The chlorine content of the product was 0.5 mg / kg, the bromine index of the product was 3472 mgBr / 100 g, the olefin removal rate was 1.9%, and the service life of the subsequent tandem clay was 7 months.

[0140] Comparative Example 4

[0141] The method of Example 2 was used to carry out dechlorination and deolefination treatment of the reforming oil, except that the deolefination catalyst A1 was replaced by an equal volume of the deolefination catalyst D1. The only difference between the catalyst D1 and the catalyst A1 was that the content of the single Pd was 0.25 wt %. The parameters are listed in Table 1.

[0142] The chlorine content of the product is 0.5 mg / kg, the bromine index of the product is 2880 mgBr / 100 g, the olefin removal rate is 18.6%, and the service life of the subsequent series-connected white clay is 8 months.

[0143] Table 1

[0144]

[0145]

[0146] Table 2

[0147]

[0148] Table 3

[0149]

[0150] According to the above data, the method disclosed in the present invention can dechlorinate and deolefinate the reforming oil in the same reactor at a lower temperature with a higher processing efficiency, and can extend the service life of the subsequent white clay; and, according to the comparison between Example 4 and Examples 1-3, when the content of the single substance Pd is within the preferred range, that is, when the content of the single substance Pd is 0.15-0.2 weight % based on the total weight of alumina, the deolefination effect is better and the service life of the subsequent white clay is longer.

[0151] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0152] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0153] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A method for dechlorination and dealkylation of reformate, characterized in that, The method includes: introducing the reformate into the first reactor of the reaction device to contact and react with a dechlorinating agent and a deolefinization catalyst; The reaction device includes the first reactor, and the first reactor includes a dechlorination treatment zone and a deolefinization treatment zone; The dechlorination treatment zone is filled with a dechlorinating agent, and the deolefinization treatment zone is filled with the deolefinization catalyst; The deolefinization catalyst includes a sulfate-containing alumina support and active components, and the active components include elemental Pd, elemental Pt, and chloride ions; Based on the total weight of alumina, the content of elemental Pd is 0.1-0.2% by weight, the content of elemental Pt is 0.01-0.15% by weight, the content of chloride ions is 0.4-2.0% by weight, and the content of sulfate is 0.4-2.0% by weight; The operating temperature of the first reactor is 35-80°C, and the contact reaction is carried out under non-hydrogen conditions; The operating pressure of the first reactor is 2.0 - 3.0 MPa, and the weight hourly space velocity of the reformate oil relative to the dechlorination agent is 5 - 10 h -1 , and the weight hourly space velocity of the reformate oil relative to the olefin removal catalyst is 15 - 25 h -1 .

2. The method according to claim 1, wherein, The dechlorinating agent is in the shape of a cylindrical strip, with a diameter of 1.5-3.5 mm, a length of 5-15 mm, a bulk density of 0.60-0.80 g / mL, a crushing strength ≥ 30 N / cm, and a breakthrough chlorine capacity ≥ 16%; The dechlorinating agent includes calcium oxide, zinc oxide, and alumina; Based on the total weight of the dechlorinating agent, the content of calcium oxide is 50-60% by weight, the content of zinc oxide is 2-10% by weight, and the content of alumina is 30-40% by weight.

3. The method according to claim 1, wherein, The volume ratio of the dechlorinating agent to the deolefinization catalyst is (1.5-2.5):

1.

4. The method according to claim 1, wherein In the deolefinization catalyst, based on the total weight of alumina, the content of sodium element is 0-0.05% by weight.

5. The method according to claim 1, wherein The specific surface area of the sulfate group-containing alumina support is 180-300 m 2 / g, the total pore volume is 0.50-1.20 cm 3 / g, and the average particle size is 1.2-1.8 mm; The specific surface area of the de-olefin catalyst is 180 - 300 m 2 / g, the total pore volume is 0.50 - 1.20 cm 3 / g, and the average particle size is 1.2 - 1.8 mm.

6. The method according to claim 5, wherein The sulfate-containing alumina support is a sulfate-containing γ-Al2O3 support.

7. The method according to claim 1, wherein, The upper end of the first reactor is provided with a reformate inlet, and the lower end of the first reactor is provided with a first treated oil outlet; The deolefinization treatment zone is closer to the reformate inlet than the dechlorination treatment zone.

8. The method according to claim 1, wherein The reaction device further includes a second reactor, a recontacting device, and a stabilizer; The second reactor is filled with clay; The reformate outlet of the recontacting device is connected to the reformate inlet; The first treated oil inlet of the stabilizer is connected to the first treated oil outlet; The second treated oil inlet of the second reactor is connected to the second treated oil outlet of the stabilizer.

9. The method according to claim 1, wherein The reformate is a full-range reformate output from the recontacting device and containing dissolved hydrogen, and the chlorine content of the reformate is 2-4 mg / Kg, and the bromine index is 2000-5000 mgBr / 100 g.

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