Reformed hydrogen dechlorinating agent as well as preparation method and application thereof

Abstract

The invention discloses a preparation method of a reforming hydrogen dechlorinating agent, which comprises the following steps: (1) drying petroleum coke, mixing with alkaline earth metal peroxide, and pretreating; (2) mixing the mixture pretreated in the step (1) with alkali, performing high-temperature treatment under an inert atmosphere condition, washing and drying; and (3) carrying out oxidation modification, washing and drying on the dried product obtained in the step (2) to obtain the dechlorinating agent. By adopting the dechlorinating agent disclosed by the invention, the content of chloride in reformed hydrogen can be reduced to 0.5 mg / L or below, and the dechlorinating agent has relatively high breakthrough chlorine capacity.

Description

Technical Field

[0001] The invention relates to the field of petrochemical industry, in particular to a reforming hydrogen dechlorination agent and a preparation method thereof and application in a reforming hydrogen dechlorination process. Background Art

[0002] In order to maintain the acidity of the reforming catalyst and adjust the "water-chlorine" balance, ethylene dichloride, trichloroethane and carbon tetrachloride are injected, resulting in a trace amount of HCl in the reformed hydrogen. At present, refineries require the hydrogen chloride content in the reformed hydrogen to be less than 1 mg / l. If the chlorine content exceeds the standard, it will have a great impact on downstream devices, especially hydrogenation devices, causing serious ammonium chloride crystallization, corroding devices and equipment, and seriously endangering the long-term operation of production devices.

[0003] At present, reforming units usually use low-temperature chemical adsorption dechlorination agents, which are non-regenerative and need to be replaced approximately every three to six months. The frequency of agent replacement is related to operating conditions, but this frequency of agent replacement still cannot avoid the occurrence of ammonium chloride crystallization in downstream units. Existing chemical adsorption dechlorination agents are prone to hardening and the hydrogen gas flow is short-range.

[0004] CN100344363C discloses an adsorbent for adsorbing hydrogen chloride impurities in gas or liquid hydrocarbon. The adsorbent comprises 25-80wt% of aluminum oxide, 1-60wt% of filler and 5-65wt% of metal oxide, wherein the filler is selected from kaolin or bentonite, and the metal oxide is selected from zinc oxide, magnesium oxide or sodium oxide. The adsorbent may further contain 0.3-5.0wt% of manganese oxide. CN106268832A discloses a dechlorinating agent, wherein the dechlorinating agent has one or more of Na2CO3, CaCO3, CaO, MgO, CuO, ZnO and their derivatives as active components, NH4HCO3 as porosity aid, at least one of Al2O3, diaspore, kaolin or kaolin as carrier and aid, and partially modified Zn salt and Ca salt as synergistic aid. CN106334516A discloses a high-pressure resistant dechlorinating agent, the raw materials of which include active components, namely, one or more composite metal oxides selected from CaO, MgO, ZnO and CuO, and pseudo-boehmite powder as a carrier. It can be seen from the above dechlorinating agent that the industry currently mainly uses chemical dechlorinating agents to remove hydrogen chloride from reforming hydrogen, but its dechlorination performance is questionable, and the product after dechlorination will be used as solid waste, which is difficult to handle.

[0005] CN109499526A discloses an activated carbon-based dechlorinating agent for removing inorganic chlorine and organic chlorine from a propylene flow and its preparation method, comprising the following components: 50-70 parts of modified activated carbon, 5-20 parts of a dechlorinating agent containing a Lewis acid center, 0-10 parts of a zeolite molecular sieve, 1-10 parts of an alkali metal or alkaline earth metal, 5-15 parts of a transition metal, 0.5-2 parts of a binder and 1-5 parts of a pore-enlarging agent; firstly mixing the powders, and then extruding, drying and calcining to obtain the activated carbon-based dechlorinating agent; the activated carbon-based dechlorinating agent has a penetration chlorine capacity of ≥15%, a saturated chlorine capacity of ≥18%, a lateral pressure strength of ≥85N / cm, and a specific surface area of ​​≥600m 2 / g, pore volume is 0.45~0.65cm 3 / g, the pile weight is ≥0.50kg / L, and the attrition is ≤3%. Among them, the modified activated carbon carrier is activated carbon treated with acid, alkali or strong oxide, and the activated carbon is one of coal-based activated carbon, coconut shell activated carbon or wood activated carbon. When this dechlorinating agent is used for reforming hydrogen dechlorination, it still belongs to the traditional chemical adsorption dechlorinating agent. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention provides a reformed hydrogen dechlorination agent and a preparation method thereof and application in a reformed hydrogen dechlorination process. The dechlorination agent of the present invention can reduce the chloride content in reformed hydrogen to below 0.5 mg / L and has a high penetration chlorine capacity.

[0007] The present invention provides a method for preparing a reforming hydrogen dechlorinating agent, comprising:

[0008] (1) drying petroleum coke, and then mixing it with alkaline earth metal peroxide, and then pre-treating it;

[0009] (2) mixing the mixture pretreated in step (1) with an alkali, subjecting it to a high temperature treatment under an inert atmosphere, washing it, and drying it;

[0010] (3) The dried product obtained in step (2) is subjected to oxidative modification, washed, and dried to obtain the dechlorinating agent.

[0011] Furthermore, in step (1), the petroleum coke is petroleum coke produced by a delayed coking unit.

[0012] Furthermore, in step (1), the conditions for drying the petroleum coke are as follows: the drying temperature is 60 to 150° C., preferably 80 to 120° C., and the drying time is 2 to 8 hours, preferably 3 to 5 hours.

[0013] Furthermore, in step (1), the alkaline earth metal is preferably one or more of magnesium, calcium and strontium.

[0014] Furthermore, in step (1), the mass ratio of the alkaline earth metal peroxide to the dried petroleum coke is 0.01:1 to 0.5:1, preferably 0.03:1 to 0.1:1.

[0015] Furthermore, in step (1), the pretreatment conditions are as follows: temperature is 200-600° C., preferably 300-500° C., and time is 2-8 h, preferably 3-5 h.

[0016] Furthermore, in step (2), the base is one or both of potassium hydroxide and sodium hydroxide.

[0017] Furthermore, in step (2), the mass ratio of the alkali to the pretreated mixture in step (1) is 0.1:1 to 5:1, preferably 0.5:1 to 3:1.

[0018] Furthermore, in step (2), the inert atmosphere is at least one of nitrogen, helium and argon.

[0019] Furthermore, in step (2), the conditions of the high temperature treatment are as follows: the temperature is 600-1000° C., preferably 700-900° C., and the treatment time is 30-180 min, preferably 60-120 min.

[0020] Furthermore, in step (3), after high temperature treatment, the sample is cooled in the presence of nitrogen, and after cooling, the sample is ground into powder for washing. The washing can be carried out using an acidic solution with a pH value not greater than 7, wherein the acid in the acidic solution is one or more of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, preferably acetic acid, and the washing is carried out until the pH value of the filtrate is neutral.

[0021] Furthermore, in step (3), the drying temperature is 60 to 150° C., preferably 80 to 120° C., and the drying time is 2 to 10 hours, preferably 4 to 8 hours.

[0022] Furthermore, in step (3), the modifier used for the oxidative modification is at least one of nitric acid, hydrogen peroxide, etc., preferably nitric acid. The concentration of the nitric acid is 0.01 to 15 mol / L, preferably 1 to 10 mol / L. The concentration of the hydrogen peroxide is 0.01 to 9 mol / L, preferably 3 to 8 mol / L. Specifically, a supersaturated impregnation method can be used, and the modification time is 0.5 to 72 hours, preferably 12 to 48 hours. The mass ratio of the modifier to the dried product obtained in step (2) is 200:1 to 0.1:1, preferably 100:1 to 20:1.

[0023] Furthermore, in step (3), the washing is performed using deionized water with a neutral washing value.

[0024] Furthermore, in step (3), the drying temperature is 60 to 150° C., preferably 80 to 120° C., and the drying time is 2 to 10 hours, preferably 4 to 8 hours.

[0025] The present invention also provides a reforming hydrogen dechlorinating agent prepared by the method.

[0026] Furthermore, the specific surface area of ​​the reforming hydrogen dechlorination agent is 800 to 3900 m 2 / g, pore volume is 0.4~2.0cm 3 / g, the most probable pore diameter is 0.6-0.8nm, and the micropore volume accounts for 70%-95% of the total pore volume.

[0027] Furthermore, in the reforming hydrogen dechlorination agent, the loading amount of the alkaline earth metal is 1 to 15 wt.%.

[0028] The present invention also provides a reforming hydrogen dechlorination method, wherein the dechlorinating agent prepared by the above method is adopted.

[0029] Furthermore, the reformed hydrogen dechlorination method comprises: the reformed hydrogen is contacted with the above-mentioned dechlorinating agent to react to obtain purified reformed hydrogen.

[0030] Furthermore, the content of hydrogen chloride in the reformed hydrogen is 0.5 to 100 mg / L, preferably 0.5 to 30 mg / L.

[0031] Furthermore, the reforming hydrogen dechlorination method adopts a fixed bed reactor. The fixed bed dechlorination conditions are: pressure 0.1-5MPa, preferably 1.5-3MPa; temperature 0-80°C, preferably 3-12°C; volume space velocity 50-5000h -1 , preferably 500~2000h -1 .

[0032] Furthermore, when the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, this is the breakthrough point, which is recorded as the breakthrough chlorine capacity.

[0033] Compared with the prior art, the dechlorinating agent of the present invention has the following advantages:

[0034] 1. In the preparation method of the reforming hydrogen dechlorinating agent of the present invention, on the one hand, in-situ synthesis technology is used to introduce the double dechlorination active center, that is, the active metal core and the oxygen-containing functional group core, into the activated carbon with high specific surface area and petroleum coke as the carbon source, so as to construct a reforming hydrogen dechlorinating agent mainly based on chemical adsorption and supplemented by physical adsorption. Since the active metal and the oxygen-containing functional group are mainly evenly distributed inside the activated carbon pores, hydrogen chloride is mainly adsorbed at the adsorption sites in the pores, and less adsorption occurs on the outer surface of the adsorbent, thereby fundamentally changing the problem that the existing chemical adsorption dechlorinating agent is easy to harden and the hydrogen gas flows short, and greatly improving the mass transfer problem. On the other hand, through pretreatment, the outer surface properties of petroleum coke are oxidatively modified in situ, so that it is more similar to the subsequent oxidation modifier used in terms of interface properties, reducing the interface energy, and thus correspondingly reducing the amount of oxidation modifier used.

[0035] 2. The method of the present invention uses petroleum coke as a carbon source and adopts a method combining alkaline earth metal oxide pre-oxidation-alkali activation-oxidation modification, which is conducive to constructing suitable stepped channels for mass transfer and diffusion of hydrogen chloride in hydrogen, is particularly suitable for reforming hydrogen dechlorination, and has a higher penetration chlorine capacity. DETAILED DESCRIPTION

[0036] The technical content and effects of the present invention are further illustrated below in conjunction with embodiments, but the present invention is not limited thereby.

[0037] In the present invention, the pore structure of the adsorbent dechlorination agent used uses the ASAP-2420M fully automatic specific surface area and pore analyzer produced by Micromeritics Corporation of the United States.

[0038] In the present invention, a fixed bed adsorber is used to evaluate the adsorption dechlorination effect, and the hydrogen chloride content in the hydrogen is measured using a microcoulometric method.

[0039] Example 1

[0040] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0041] (1) Petroleum coke was dried at 100°C for 4 h, and then mixed with calcium peroxide at a mass ratio of 0.1:1 and pretreated. The pretreatment conditions were as follows: temperature 450°C, time 4 h;

[0042] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:2, subjecting the mixture to a high temperature treatment under nitrogen (temperature of 800° C. for 80 min), washing the mixture with acetic acid until the pH value of the filtrate is neutral, and drying the mixture at 100° C. for 6 h;

[0043] (3) Using nitric acid with a concentration of 10 mol / L as an oxidizing modifier, the dried product obtained in step (2) is oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) is 70:1, and the modification time is 24 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent A-1.

[0044] The specific surface area of ​​reforming hydrogen dechlorination agent A-1 is 2100m 2 / g, pore volume is 1.25cm 3 / g, the most probable pore diameter is 0.65nm, and the micropore volume is 1.09cm 3 / g.

[0045] Evaluation of reforming hydrogen dechlorination agent A-1: ​​A fixed bed reactor was used, the hydrogen chloride content in the reforming hydrogen was 30 mg / L, and the dechlorination conditions were: operating pressure 2 MPa, temperature 8 °C, volume space velocity 2000 h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as Q C -1.

[0046] Example 2

[0047] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0048] (1) The petroleum coke was dried at 100°C for 4 h, and then mixed with strontium peroxide at a mass ratio of 0.05:1 and pretreated. The pretreatment conditions were as follows: temperature was 500°C and time was 5 h;

[0049] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:3, subjecting it to high temperature treatment under nitrogen conditions (temperature of 900° C., treatment time of 120 min), washing it with hydrochloric acid until the pH value of the filtrate is neutral, and drying it at 100° C. for 6 h;

[0050] (3) Using nitric acid with a concentration of 8 mol / L as an oxidizing modifier, the dried product obtained in step (2) is oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) is 100:1, and the modification time is 12 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent A-2.

[0051] The specific surface area of ​​reforming hydrogen dechlorination agent A-2 is 3100m 2 / g, pore volume is 1.55cm 3 / g, the most probable pore diameter is 0.68nm, and the micropore volume is 1.41cm 3 / g.

[0052] Evaluation of reforming hydrogen dechlorination agent A-2: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 2MPa, temperature 8℃, volume space velocity 2000h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as Q C -2.

[0053] Example 3

[0054] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0055] (1) The petroleum coke was dried at 100°C for 4 h, and then mixed with magnesium peroxide at a mass ratio of 0.03:1 and pretreated. The pretreatment conditions were as follows: temperature 400°C, time 3 h;

[0056] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:1, subjecting the mixture to a high temperature treatment under nitrogen (temperature of 700° C. for 60 min), washing the mixture with acetic acid until the pH value of the filtrate is neutral, and drying the mixture at 100° C. for 6 h;

[0057] (3) Using hydrogen peroxide with a concentration of 8 mol / L as an oxidative modifier, the dried product obtained in step (2) was oxidatively modified (supersaturated impregnation method, the mass ratio of hydrogen peroxide to the dried product was 100:1, and the modification time was 48 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent A-3.

[0058] The specific surface area of ​​reforming hydrogen dechlorination agent A-3 is 1300m 2 / g, pore volume is 0.65cm 3 / g, the most probable pore diameter is 0.60nm, and the micropore volume is 0.59cm 3 / g.

[0059] Evaluation of reforming hydrogen dechlorination agent A-3: A fixed bed reactor was used, the hydrogen chloride content in the reforming hydrogen was 30 mg / L, and the dechlorination conditions were: operating pressure 2 MPa, temperature 8 °C, volume space velocity 2000 h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as Q C -3.

[0060] Example 4

[0061] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0062] (1) The petroleum coke was dried at 100°C for 4 hours, and then mixed with calcium peroxide and magnesium peroxide in a mass ratio of 0.1:1, wherein the mass ratio of calcium peroxide to magnesium peroxide was 1:1, and pretreated. The pretreatment conditions were as follows: temperature of 500°C and time of 4 hours;

[0063] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:1, subjecting it to high temperature treatment under nitrogen conditions (temperature 900° C., treatment time 120 min), washing it with acetic acid until the pH value of the filtrate is neutral, and drying it at 100° C. for 6 h;

[0064] (3) Using nitric acid with a concentration of 10 mol / L as an oxidizing modifier, the dried product obtained in step (2) is oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) is 30:1, and the modification time is 24 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent A-4.

[0065] The specific surface area of ​​reforming hydrogen dechlorination agent A-4 is 1091m 2 / g, pore volume is 0.59cm 3 / g, the most probable pore diameter is 0.61nm, and the micropore volume is 0.42cm 3 / g.

[0066] Evaluation of reforming hydrogen dechlorination agent A-4: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 2MPa, temperature 8℃, volume space velocity 2000h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as Q C -4.

[0067] Example 5

[0068] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0069] (1) petroleum coke is dried at 100°C for 4 hours, and then mixed with calcium peroxide and strontium peroxide in a mass ratio of 0.1:1, wherein the mass ratio of calcium peroxide to strontium peroxide is 1:1, and pretreated. The pretreatment conditions are as follows: temperature is 500°C, and time is 5 hours;

[0070] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:3, subjecting it to high temperature treatment under nitrogen conditions (temperature 900° C., treatment time 120 min), washing it with acetic acid until the pH value of the filtrate is neutral, and drying it at 100° C. for 6 h;

[0071] (3) Using nitric acid with a concentration of 9 mol / L as an oxidizing modifier, the dried product obtained in step (2) was oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) was 90:1, and the modification time was 36 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent A-5.

[0072] The specific surface area of ​​reforming hydrogen dechlorination agent A-5 is 3317m 2 / g, pore volume is 1.71cm 3 / g, the most probable pore diameter is 0.71nm, and the micropore volume is 1.59cm 3 / g.

[0073] Evaluation of reforming hydrogen dechlorination agent A-5: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 2MPa, temperature 8℃, volume space velocity 2000h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as Q C -5.

[0074] Example 6

[0075] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0076] (1) Petroleum coke was dried at 100°C for 4 h, and then mixed with calcium peroxide at a mass ratio of 0.1:1 and pretreated. The pretreatment conditions were as follows: temperature 450°C, time 4 h;

[0077] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:2, subjecting the mixture to a high temperature treatment under nitrogen (temperature of 800° C. for 80 min), washing the mixture with acetic acid until the pH value of the filtrate is neutral, and drying the mixture at 100° C. for 6 h;

[0078] (3) Using nitric acid with a concentration of 10 mol / L as an oxidizing modifier, the dried product obtained in step (2) is oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) is 70:1, and the modification time is 24 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent A-6.

[0079] The specific surface area of ​​reforming hydrogen dechlorination agent A-6 is 2100m 2 / g, pore volume is 1.25cm 3 / g, the most probable pore diameter is 0.65nm, and the micropore volume is 1.09cm 3 / g.

[0080] Evaluation of reforming hydrogen dechlorination agent A-6: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 1.5 MPa, temperature 8°C, volume space velocity 500 h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as Q C -6.

[0081] Comparative Example 1

[0082] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0083] (1) Anthracite was dried at 100°C for 4 h, mixed with calcium peroxide and strontium peroxide in a mass ratio of 0.1:1, wherein the mass ratio of calcium peroxide to strontium peroxide was 1:1, and pretreated under the following conditions: temperature of 500°C and time of 5 h;

[0084] (2) mixing the mixture pretreated in step (1) with potassium hydroxide in a mass ratio of 1:3, subjecting the mixture to a high temperature treatment under nitrogen (temperature of 900° C. for 120 min), washing the mixture with acetic acid until the pH value of the filtrate is neutral, and drying the mixture at 100° C. for 6 h;

[0085] (3) Using nitric acid with a concentration of 9 mol / L as an oxidizing modifier, the dried product obtained in step (2) was oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) was 90:1, and the modification time was 36 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent B-1.

[0086] The specific surface area of ​​reforming hydrogen dechlorination agent B-1 is 775m 2 / g, pore volume is 0.39cm 3 / g, the most probable pore diameter is 0.51nm, and the micropore volume is 0.35cm 3 / g.

[0087] Evaluation of reforming hydrogen dechlorination agent B-1: A fixed bed reactor was used, the hydrogen chloride content in the reforming hydrogen was 30 mg / L, and the dechlorination conditions were: operating pressure 2 MPa, temperature 8 °C, volume space velocity 2000 h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as D C -1.

[0088] Comparative Example 2

[0089] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0090] (1) The petroleum coke was dried at 100°C for 4 h, then mixed with potassium hydroxide and silver oxide in a mass ratio of 1:3:0.1, and subjected to high temperature treatment under nitrogen conditions (temperature of 900°C, treatment time of 60 min), washed with acetic acid until the pH value of the filtrate was neutral, and dried at 100°C for 6 h;

[0091] (2) The sample was cooled under nitrogen protection, ground into powder after cooling, washed with 10 wt% acetic acid solution, washed with deionized water until the pH value of the filtrate was neutral, and then dried at 120°C for 6 h to obtain an activated carbon intermediate.

[0092] (3) Take the obtained activated carbon intermediate and perform oxidation modification at room temperature using a gas with a volume content of 5% oxygen (carrier gas is nitrogen). The modification time is 6 h and the volume space velocity is 100 h -1 , and then purged with nitrogen at a space velocity of 100 h -1 The specific surface area of ​​the prepared adsorbent is 2900m 2 / g, the pore volume is 1.09cm3 / g, the most probable pore diameter is 0.6-0.7nm, and the dechlorination agent B-2 is obtained.

[0093] Evaluation of reforming hydrogen dechlorination agent B-2: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 2MPa, temperature 8℃, volume space velocity 2000h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as D C -2.

[0094] Comparative Example 3

[0095] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0096] (1) The petroleum coke was dried at 100°C for 4 h, then treated with potassium hydroxide at a mass ratio of 1:3 under nitrogen conditions at a high temperature (temperature of 900°C for 60 min), washed with acetic acid until the pH value of the filtrate was neutral, and dried at 100°C for 6 h;

[0097] (2) The activated carbon obtained in step (1) is dried at 100° C. for 4 h, and then mixed with calcium peroxide and strontium peroxide in a mass ratio of 0.1:1, wherein the mass ratio of calcium peroxide to strontium peroxide is 1:1, and pretreated under the following conditions: temperature of 500° C. for 5 h, washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorination agent B-3.

[0098] The specific surface area of ​​reforming hydrogen dechlorination agent B-3 is 2310m 2 / g, pore volume is 0.81cm 3 / g, and the most probable pore size is 1.1nm.

[0099] Evaluation of reforming hydrogen dechlorination agent B-3: A fixed bed reactor was used, the hydrogen chloride content in the reforming hydrogen was 30 mg / L, and the dechlorination conditions were: operating pressure 2 MPa, temperature 8 °C, volume space velocity 2000 h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as D C -3.

[0100] Comparative Example 4

[0101] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0102] (1) The petroleum coke was dried at 100°C for 4 h, the petroleum coke was mixed with potassium hydroxide and magnesium hydroxide in a mass ratio of 1:2:0.1, and subjected to high temperature treatment under nitrogen conditions (temperature of 800°C, treatment time of 80 min), washed with acetic acid until the pH value of the filtrate was neutral, and dried at 100°C for 6 h;

[0103] (2) Using nitric acid with a concentration of 10 mol / L as an oxidizing modifier, the dried product obtained in step (2) was oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) was 70:1, and the modification time was 24 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent B-4.

[0104] The specific surface area of ​​reforming hydrogen dechlorination agent B-4 is 1819m 2 / g, pore volume is 0.91cm 3 / g, the most probable pore diameter is 0.51nm, and the micropore volume is 0.71cm 3 / g.

[0105] Evaluation of reforming hydrogen dechlorination agent B-4: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 2MPa, temperature 8℃, volume space velocity 2000h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as D C -4.

[0106] Comparative Example 5

[0107] The preparation method of the reforming hydrogen dechlorinating agent in this example comprises:

[0108] (1) Petroleum coke was dried at 100°C for 4 h, the reaction temperature was 70°C, the pressure was 2 atm, ozone was used, and the volumetric space velocity was 1000 h -1The oxidation treatment time is 8 hours. The oxidized product is then washed with water until neutral and dried at 120°C for 6 hours.

[0109] (2) mixing the oxidized petroleum coke pretreated in step (1) with potassium hydroxide and magnesium hydroxide in a mass ratio of 1:2:0.1, subjecting the mixture to a high temperature treatment (temperature of 800° C. for 80 min) under nitrogen conditions, washing the mixture with acetic acid until the pH value of the filtrate is neutral, and drying the mixture at 100° C. for 6 h;

[0110] (3) Using nitric acid with a concentration of 10 mol / L as an oxidizing modifier, the dried product obtained in step (2) was oxidatively modified (supersaturated impregnation method, the mass ratio of nitric acid to the dried product in step (2) was 70:1, and the modification time was 24 h), washed with deionized water until neutral, and dried at 100° C. for 6 h to obtain the dechlorinating agent B-5.

[0111] The specific surface area of ​​reforming hydrogen dechlorination agent B-5 is 1916m 2 / g, pore volume is 1.01cm 3 / g, the most probable pore diameter is 0.59nm, and the micropore volume is 0.85cm 3 / g.

[0112] Evaluation of reforming hydrogen dechlorination agent B-5: Using a fixed bed reactor, the hydrogen chloride content in the reforming hydrogen is 30 mg / L, and the dechlorination conditions are: operating pressure 2MPa, temperature 8℃, volume space velocity 2000h -1 When the hydrogen chloride content at the outlet of the fixed bed reactor is greater than 0.5 mg / L, the breakthrough chlorine capacity is recorded as D C -5.

[0113] Table 1 Dechlorination effect of the dechlorinating agent obtained in each example

[0114]

[0115]

[0116] The embodiments of the present invention are only detailed descriptions of the technical solutions of the present invention, but the present invention is not limited to the above embodiments, that is, the present invention can be implemented without relying on the steps described in the above embodiments. In summary, any improvements made to the present invention by those skilled in the art, as long as they do not deviate from the content of the technical solutions of the present invention, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention, shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a reforming hydrogen dechlorinating agent, comprising: (1) drying petroleum coke, and then mixing it with alkaline earth metal peroxide, and then pre-treating it; (2) mixing the mixture pretreated in step (1) with an alkali, subjecting it to a high temperature treatment under an inert atmosphere, washing it, and drying it; (3) The dried product obtained in step (2) is subjected to oxidative modification, washed, and dried to obtain the dechlorinating agent.

2. The method according to claim 1, characterized in that In step (1), the conditions for drying the petroleum coke are as follows: the drying temperature is 60-150°C, preferably 80-120°C, and the drying time is 2-8h, preferably 3-5h; and / or, in step (3), the drying temperature is 60-150°C, preferably 80-120°C, and the drying time is 2-10h, preferably 4-8h.

3. The method according to claim 1, characterized in that In step (1), the alkaline earth metal is one or more of magnesium, calcium and strontium.

4. The method according to claim 1, characterized in that: In step (1), the mass ratio of the alkaline earth metal peroxide to the dried petroleum coke is 0.01:1 to 0.5:1, preferably 0.03:1 to 0.1:1; and / or, in step (1), the pretreatment conditions are as follows: the temperature is 200 to 600°C, preferably 300 to 500°C, and the time is 2 to 8 hours, preferably 3 to 5 hours.

5. The method according to claim 1, characterized in that: In step (2), the alkali is one or both of potassium hydroxide and sodium hydroxide; and / or, in step (2), the mass ratio of the alkali to the pretreated mixture in step (1) is 0.1:1 to 5:1, preferably 0.5:1 to 3:1; and / or, in step (2), the conditions of the high temperature treatment are as follows: the temperature is 600 to 1000° C., preferably 700 to 900° C., and the treatment time is 30 to 180 min, preferably 60 to 120 min.

6. The method according to claim 1, characterized in that In step (3), washing is performed using an acidic solution having a pH value not greater than 7, wherein the acid in the acid solution is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, preferably acetic acid, and washing is performed until the pH value of the filtrate is neutral; and / or, in step (3), the drying temperature is 60 to 150° C., preferably 80 to 120° C., and the drying time is 2 to 10 hours, preferably 4 to 8 hours.

7. The method according to claim 1, characterized in that In step (3), the modifier used for the oxidative modification is at least one of nitric acid and hydrogen peroxide; preferably, the concentration of the nitric acid is 0.01 to 15 mol / L, preferably 1 to 10 mol / L, and the concentration of the hydrogen peroxide is 0.01 to 9 mol / L, preferably 3 to 8 mol / L; further preferably, the oxidative modification in step (3) adopts a supersaturated impregnation method, the modification time is 0.5 to 72 h, preferably 12 to 48 h, and the mass ratio of the modifier to the dried product obtained in step (2) is 200:1 to 0.1:1, preferably 100:1 to 20:

1.

8. A reforming hydrogen dechlorinating agent prepared by the method according to any one of claims 1 to 7.

9. The reforming hydrogen dechlorination agent according to claim 8, characterized in that The specific surface area of ​​the reforming hydrogen dechlorination agent is 800 to 3900 m 2 / g, pore volume is 0.4~2.0cm 3 / g, the most probable pore diameter is 0.6-0.7nm, and the micropore volume accounts for 70%-95% of the total pore volume.

10. The reforming hydrogen dechlorination agent according to claim 8, characterized in that In the reforming hydrogen dechlorination agent, the loading amount of the alkaline earth metal is 5wt% to 20wt%.

11. A method for dechlorinating reformed hydrogen, characterized in that: The dechlorinating agent according to any one of claims 8 to 10 is used.

12. The method according to claim 11, characterized in that The content of hydrogen chloride in the reformed hydrogen is 0.5 to 100 mg / L, preferably 0.5 to 30 mg / L.

13. The method according to claim 11, characterized in that The reforming hydrogen dechlorination method adopts a fixed bed reactor, wherein the fixed bed dechlorination conditions are: pressure 0.1-5MPa, preferably 1.5-3MPa; temperature 0-80°C, preferably 3-12°C; volume space velocity 50-5000h -1 , preferably 500~2000h -1 .

Images