CN110885699A - Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof - Google Patents

Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof Download PDF

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CN110885699A
CN110885699A CN201811044658.7A CN201811044658A CN110885699A CN 110885699 A CN110885699 A CN 110885699A CN 201811044658 A CN201811044658 A CN 201811044658A CN 110885699 A CN110885699 A CN 110885699A
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dechlorination
sodium carbonate
pore volume
dechlorinating agent
pore diameter
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CN110885699B (en
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王继元
王彩杰
堵文斌
孟海
王亚明
杨爱武
朱庆奋
柏基业
刘建新
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a dechlorinating agent with large pore volume and pore diameter, a preparation method and application thereof, wherein the dechlorinating agent consists of sodium carbonate and aluminum oxide; wherein the mass content of the sodium carbonate is 5-30%, and the mass content of the alumina is 70-95%; the pore volume of the dechlorinating agent is 0.5-1.5 cm3(ii)/g, the average pore diameter is 5 to 30 nm. The dechlorination agent has stable pore structure and large pore volume and pore diameter, and can realize higher dechlorination efficiency and dechlorination precision when being used for liquid-phase dechlorination of reformed oil; the preparation process of the dechlorinating agent is simple and easy to realize industrial production; the dechlorinating agent does not contain heavy metals or metals which are not friendly to the environment, has low preparation cost and does not pollute the environment.

Description

Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a dechlorinating agent with large pore volume and pore diameter, and a preparation method and application thereof.
Background
The catalytic reforming is a process of converting a light gasoline fraction obtained by distilling raw oil into high-octane gasoline rich in aromatic hydrocarbons and by-producing liquefied petroleum gas and hydrogen under the action of heating, hydrogen and a catalyst. In order to ensure the catalytic performance of the catalytic reforming catalyst, the reformed raw oil needs to be subjected to hydrogenation pre-refining, but as various chloralkane auxiliaries are added in the process of extracting the raw oil, organic chloride can be converted into HCl in the process of hydrogenation pre-refining of the raw oil, so that the HCl becomes a main source of HCl in the reforming process. In addition, the catalyst is gradually reduced in activity during use, and thus, in order to maintain the activity of the catalyst, chlorine needs to be continuously supplemented, so that a certain amount of HCl is contained in the gas generated in the reforming process. In order to eliminate the influence of hydrogen chloride, the method for removing hydrogen chloride in the generated oil by using a dechlorinating agent is a common method at present. In recent years, a solid dechlorinating agent is generally adopted in industrial devices to remove hydrogen chloride in reformed oil, and the dechlorinating mechanism is that active components in the dechlorinating agent and HCL are sent to carry out acid-base neutralization reaction to generate stable metal chloride to be fixed, so that the aim of removing HCL is fulfilled. The active component is usually selected from alkali metal or alkaline earth metal oxide capable of reacting with HCL, and then the active component and the binder are prepared into dechlorinating agent by a kneading method, or the active component is loaded on the carrier by an impregnation method, such as:
chinese patent CN105542836A discloses a high-precision liquid-phase dechlorinating agent for liquid-phase dechlorination of reformate, which consists of the following components: 5-20% of CuO, 5-10% of CaO, 4-8% of KOH and the balance of modified activated carbon. The preparation method comprises the steps of dipping the modified activated carbon into a Cu-Ca composite solution, filtering, draining, roasting, dipping a roasted product into a KOH aqueous solution, filtering and drying to obtain the dechlorinating agent. The chlorine capacity of the obtained dechlorinating agent is more than 16 percent, and the dechlorinating precision is less than 0.5 ppm.
Chinese patent CN104437342A discloses a high-chlorine-capacity liquid-phase dechlorinating agent, a preparation method and application thereof, which are suitable for removing hydrogen chloride in reformed oil. The carrier of the dechlorinating agent is a carbon molecular sieve, the active component is an oxide of alkali metal and alkaline earth metal, and the auxiliary agent component is copper oxide, iron oxide or zinc oxide. The preparation method comprises soaking soluble copper salt, calcium salt, magnesium salt, barium salt, etc. onto cylindrical carbon molecular sieve, drying, and stabilizing. The chlorine capacity of the dechlorinating agent is 26-33%, and the dechlorinating agent is good in water resistance.
Chinese patent CN 105478000 a discloses a dechlorinating agent for purifying reformed regeneration gas and a preparation method thereof, wherein the dechlorinating agent comprises 85-90 wt% of composite oxide carrier and 10-15 wt% of alkaline earth metal oxide. The preparation method comprises the steps of mixing soluble aluminum salt and silica sol into Al-Si mixed liquor, adding soluble zirconium salt into the Al-Si mixed liquor, stirring, aging, filtering, drying and roasting to obtain a composite oxide carrier, soaking the composite oxide carrier in soluble salt solution of alkaline earth metal, and then filtering, drying and roasting to obtain the dechlorinating agent. The penetrating chlorine capacity of the obtained dechlorinating agent can reach more than 68 percent at most.
In the prior art, as in the above-mentioned CN105542836A and CN104437342A, dechlorinating agents are prepared by using activated carbon as a carrier, and the loss of metal components is easily caused due to weak binding force between the activated carbon and the active metal components. The traditional method for dechlorinating the oil phase generated by reforming adopts a fixed bed dechlorinating process, the particles of the dechlorinating agent are large (3-5 mm), the pore volume and the pore diameter of the liquid-phase dechlorinating agent developed at home and abroad at present are small, the average pore diameter of the dechlorinating agent in the Chinese patent CN105542836A is 1.3-2.0 nm, and the pore volume is below 0.8 mL/g; the average pore diameter of the carbon molecular sieve of the Chinese patent CN104437342A is 0.6-0.7 nm; the dechlorinating agent of the Chinese patent CN 105478000A has an average pore diameter of 7-9 nm and a pore volume of 0.5-0.7 cm3G, nowWhen the solid dechlorinating agent is used for liquid-phase dechlorination of reformed oil, the dechlorinating agent has low dechlorinating efficiency and low dechlorinating precision due to small pore volume and pore diameter, large particles and high liquid-phase mass transfer resistance. Therefore, how to improve the dechlorination efficiency and dechlorination accuracy of the liquid-phase dechlorination of the reformate still remains a problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems of low dechlorination efficiency and low dechlorination precision caused by large mass transfer resistance and low mass transfer efficiency when the solid dechlorination agent is used for liquid-phase dechlorination of reformed oil in the prior art, the invention aims to provide the dechlorination agent with large pore volume and pore diameter; the other purpose is to provide a preparation method of the dechlorinating agent; the invention also provides an application method of the dechlorinating agent.
In order to realize the first purpose of the invention, the invention adopts the technical scheme that: a dechlorinating agent with large pore volume and pore diameter, which consists of sodium carbonate and aluminum oxide; wherein the mass content of the sodium carbonate is 5-30%, and the mass content of the alumina is 70-95%; the pore volume of the dechlorinating agent is 0.5-1.5 cm3(ii)/g, the average pore diameter is 5 to 30 nm.
The dechlorination agent takes sodium carbonate as an active component and alumina as a carrier, and the binding force between the sodium carbonate and the alumina is stronger, so that the technical problem that metal components are easy to lose due to weak binding force between the active carbon and the active metal components in the dechlorination agent taking the active carbon as the carrier in the prior art is solved. The alumina is used as a carrier to prepare the alumina with the pore volume of 0.5-1.5 cm3A dechlorinating agent with a large pore volume and a large pore diameter, wherein the dechlorinating agent has an average pore diameter of 5-30 nm.
In order to improve the dechlorination performance of the dechlorination agent, the pore volume of the dechlorination agent is further preferably 0.8-1.2 cm3(ii)/g, the average pore diameter is 10 to 20 nm.
In order to improve the dechlorinating performance of the dechlorinating agent, the dechlorinating agent preferably comprises 10-20% by mass of sodium carbonate and 80-90% by mass of aluminum oxide.
In order to achieve the second object of the invention, the invention adopts the technical scheme that: a preparation method of the dechlorinating agent comprises the following steps:
(1) the pore volume is 1.0-1.5 cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 10-30 nm at 400-1000 ℃ to obtain alumina powder, and cooling to room temperature for later use;
(2) preparing solid sodium carbonate into a sodium carbonate aqueous solution, and cooling to room temperature for later use;
(3) uniformly mixing the alumina powder obtained in the step (1), aluminum hydroxide powder and a cellulose binder to obtain a mixed material; the pore volume and the aperture of the aluminum hydroxide powder are smaller than those of the aluminum oxide powder.
(4) And (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material obtained in the step (3), kneading uniformly, and obtaining the dechlorinating agent after extrusion molding, drying and roasting.
Macroporous pseudo-boehmite, also known as alumina monohydrate, pseudoboehmite, molecular formula: AlOOH & nH 2O, wherein n is 0.08-0.62, is commonly called as alumina dry glue powder, is nontoxic, tasteless, odorless and white powder, has the characteristics of high purity, high specific surface area, uniform pore size distribution, large pore volume, good water absorption, good dispersibility, good thermal stability, good wear resistance and the like, and has good forming performance. The invention firstly makes the pore volume of 1.0-1.5 cm3And (2) roasting the macroporous pseudo-boehmite powder with the average pore diameter of 10-30 nm at 400-1000 ℃ to obtain large-pore volume and large-pore diameter alumina powder with stable pore structure, which is beneficial to maintaining the inherent large pore volume and large pore diameter of the alumina powder in the subsequent kneading and extrusion molding process and is very beneficial to reducing the liquid phase mass transfer resistance. By adopting the compounding of part of the small-pore aluminum hydroxide powder and the cellulose binder with the large-pore-volume and large-pore-diameter alumina powder, on one hand, the extrusion performance of the alumina powder can be improved, on the other hand, the dechlorinating agent can play a role in pore volume and pore diameter uniformity, and the cellulose binder can volatilize in the roasting process and also has a hole expansion function, thereby being beneficial to uniform pore volume and pore diameter uniformity. The invention prepares solid sodium carbonate into aqueous solution, and the aqueous solution is dripped and kneaded into a mixed material of alumina powder, aluminum hydroxide powder and cellulose binderThe mode of the dechlorinating agent enables the uniformity of the sodium carbonate loaded on the carrier to be high, is beneficial to the full reaction of active components of the sodium carbonate in the dechlorinating reaction process, and improves the utilization rate of the dechlorinating agent.
In order to prepare a dechlorinating agent with higher dechlorinating performance, the mass concentration of the sodium carbonate aqueous solution in the step (2) is preferably 5-25%.
In order to prepare a dechlorinating agent with higher dechlorinating performance, the mass ratio of the alumina powder, the aluminum hydroxide powder and the binder in the step (3) is preferably as follows: 100: 10-30: 1 to 3.
In order to prepare a dechlorinating agent with higher dechlorinating performance, the pore volume of the aluminum hydroxide powder in the step (3) is preferably 0.3-0.5 cm3The average pore diameter is 3-10 nm; the cellulose binder is hydroxypropyl methylcellulose.
In order to prepare a dechlorinating agent with higher dechlorinating performance, the roasting temperature in the step (4) is preferably 300-600 ℃, and the roasting time is preferably 1-10 hours. The pore structure of the dechlorinating agent is fixed through high-temperature roasting in the last step, so that the dechlorinating agent cannot be broken due to high stacking pressure in the later application process.
In order to achieve the third object of the invention, the invention adopts the technical scheme that: and dechlorinating the dechlorinating agent in a liquid phase for the reformed oil, wherein the mass concentration of chlorine in the reformed oil is 10-100 ppm.
When the dechlorinating agent is used for liquid-phase dechlorination of reformed oil, the process conditions of the dechlorination reaction are as follows: the reaction temperature is 20-120 ℃; the liquid hourly space velocity is 0.5-10 h-1(ii) a The reaction pressure is 0.1-1 MPa.
The dechlorinating agent is suitable for removing inorganic chlorine in oil products, especially for removing hydrogen chloride in reformed oil, and is also suitable for fine dechlorination in chemical production such as synthetic ammonia, methanol, bi-alcohol, methanation and the like, and the application range is wide.
The invention has the beneficial effects that: compared with the prior art, the dechlorination agent has the advantages that the pore structure is stable, the pore volume and the pore diameter are large, and high dechlorination efficiency and dechlorination precision can be obtained in the liquid-phase dechlorination process; the dechlorinating agent has simple preparation process and is easy to realize industrial production; the dechlorinating agent does not contain precious or environment-unfriendly metal, and has simple preparation cost and no environmental pollution.
Detailed Description
Description of the drawings:
the reformate used in the following examples, experimental examples and comparative examples was obtained from the petrochemical company Yangzi, Inc., China.
The raw materials used in the following examples, experimental examples and comparative examples are commercially available.
The dechlorinating agents obtained in the following examples and comparative examples were tested for pore volume and pore size according to the BET method.
The chlorine contents before and after dechlorination of the reformate used in the following examples and comparative examples were measured by reference to GB/T18612-2011.
Example 1
(1) The pore volume was 1.5cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 30nm at 400 ℃ for 4h to obtain alumina powder, and cooling to room temperature for later use;
(2) dissolving solid sodium carbonate in deionized water to prepare a sodium carbonate aqueous solution with the mass concentration of 5%, and cooling to room temperature for later use;
(3) uniformly mixing 100 parts of the alumina powder obtained in the step (1), 10 parts of small-hole aluminum hydroxide powder and 1 part of hydroxypropyl methyl cellulose binder to obtain a mixed material; the pore volume of the small-pore aluminum hydroxide powder is 0.3cm3(ii)/g, average pore diameter of 3 nm;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material, kneading uniformly, extruding and molding, drying at 100 ℃ for 2h, and roasting at 300 ℃ for 10h to obtain the dechlorinating agent.
The dechlorinating agent obtained in the example comprises 5% by mass of sodium carbonate, 95% by mass of alumina and 1.5cm of pore volume3In g, the mean pore diameter is 30 nm.
Example 2
(1) The pore volume was set to 1.0cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 10nm at 1000 ℃ for 4 hours to obtain alumina powder, and cooling to room temperature for later use;
(2) dissolving solid sodium carbonate in deionized water to prepare a sodium carbonate aqueous solution with the mass concentration of 25%, and cooling to room temperature for later use;
(3) uniformly mixing 100 parts of the alumina powder obtained in the step (1), 30 parts of small-hole aluminum hydroxide powder and 3 parts of hydroxypropyl methyl cellulose binder to obtain a mixed material; the pore volume of the small-pore aluminum hydroxide powder is 0.5cm3(ii)/g, average pore diameter of 10 nm;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material, kneading uniformly, extruding and molding, drying at 100 ℃ for 2h, and roasting at 600 ℃ for 1h to obtain the dechlorinating agent.
The dechlorinating agent obtained in the example comprises 30% by mass of sodium carbonate, 70% by mass of alumina and 0.5cm of pore volume3In terms of/g, the mean pore diameter is 5 nm.
Example 3
(1) The pore volume was set to 1.3cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 25nm at 600 ℃ for 4 hours to obtain alumina powder, and cooling to room temperature for later use;
(2) dissolving solid sodium carbonate in deionized water to prepare a sodium carbonate aqueous solution with the mass concentration of 10%, and cooling to room temperature for later use;
(3) uniformly mixing 100 parts of the alumina powder obtained in the step (1), 15 parts of small-hole aluminum hydroxide powder and 1.5 parts of hydroxypropyl methyl cellulose binder to obtain a mixed material; the pore volume of the small-pore aluminum hydroxide powder is 0.4cm3(ii)/g, average pore diameter of 5 nm;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material, kneading uniformly, extruding and molding, drying at 100 ℃ for 2h, and roasting at 600 ℃ for 3h to obtain the dechlorinating agent.
The dechlorinating agent obtained in the example comprises 10% by mass of sodium carbonate, 90% by mass of alumina and 1.2cm of pore volume3In g, the mean pore diameter is 20 nm.
Example 4
(1) The pore volume was 1.1cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 15nm at 800 ℃ for 4h to obtain alumina powderCooling to room temperature;
(2) dissolving solid sodium carbonate in deionized water to prepare a sodium carbonate aqueous solution with the mass concentration of 20%, and cooling to room temperature for later use;
(3) uniformly mixing 100 parts of the alumina powder obtained in the step (1), 25 parts of small-hole aluminum hydroxide powder and 1 part of hydroxypropyl methyl cellulose binder to obtain a mixed material; the pore volume of the small-pore aluminum hydroxide powder is 0.5cm3(ii)/g, average pore diameter of 10 nm;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material, kneading uniformly, extruding and molding, drying at 100 ℃ for 2h, and roasting at 500 ℃ for 4h to obtain the dechlorinating agent.
The dechlorinating agent obtained in the embodiment comprises 20% by mass of sodium carbonate, 80% by mass of aluminum oxide and 0.8cm of pore volume3In g, the mean pore diameter is 10 nm.
Example 5
(1) The pore volume was set to 1.3cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 25nm at 700 ℃ for 4h to obtain alumina powder, and cooling to room temperature for later use;
(2) dissolving solid sodium carbonate in deionized water to prepare a sodium carbonate aqueous solution with the mass concentration of 20%, and cooling to room temperature for later use;
(3) uniformly mixing 100 parts of the alumina powder obtained in the step (1), 20 parts of small-hole aluminum hydroxide powder and 10 parts of hydroxypropyl methyl cellulose binder to obtain a mixed material; the pore volume of the small-pore aluminum hydroxide powder is 0.5cm3(ii)/g, average pore diameter of 10 nm;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material, kneading uniformly, extruding and molding, drying at 100 ℃ for 2h, and roasting at 450 ℃ for 4h to obtain the dechlorinating agent.
The dechlorinating agent obtained in the example comprises 15% by mass of sodium carbonate, 85% by mass of alumina and 1.0cm of pore volume3In g, the mean pore diameter is 16 nm.
Example 6
(1) The pore volume was 1.2cm3Macroporous pseudo-boehmite powder with average pore diameter of 22nmRoasting the alumina powder at 650 ℃ for 4h to obtain alumina powder, and cooling to room temperature for later use;
(2) dissolving solid sodium carbonate in deionized water to prepare a sodium carbonate aqueous solution with the mass concentration of 18%, and cooling to room temperature for later use;
(3) uniformly mixing 100 parts of the alumina powder obtained in the step (1), 25 parts of small-hole aluminum hydroxide powder and 2 parts of hydroxypropyl methyl cellulose binder to obtain a mixed material; the pore volume of the small-pore aluminum hydroxide powder is 0.5cm3(ii)/g, average pore diameter of 10 nm;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material, kneading uniformly, extruding and molding, drying at 100 ℃ for 2h, and roasting at 450 ℃ for 4h to obtain the dechlorinating agent.
The dechlorinating agent obtained in the example comprises 18% by mass of sodium carbonate, 82% by mass of alumina and 0.9cm of pore volume3In g, the mean pore diameter is 14 nm.
Comparative example 1
Substantially the same as in example 5 except that the step (1) was omitted and 100 parts of the cells were directly charged to a volume of 1.3cm3And (3) uniformly mixing alumina powder with the average pore diameter of 25nm, 20 parts of small-pore aluminum hydroxide powder and 10 parts of hydroxypropyl methyl cellulose binder to obtain a mixed material.
The dechlorinating agent obtained in the comparative example comprises 15% by mass of sodium carbonate, 85% by mass of aluminum oxide and 0.5cm of pore volume3G, average pore diameter of 7 nm.
Comparative example 2
The dechlorinating agent is prepared according to the method provided by Chinese patent CN105542836A (a high-precision liquid-phase dechlorinating agent and a preparation method thereof), and comprises the following components: 10% of CuO, 10% of CaO, 5% of KOH and the balance of modified activated carbon.
The dechlorinating agent obtained in the comparative example had a pore volume of 0.3cm3In g, the average pore diameter is 2 nm.
Example 7
The reformate with the hydrogen chloride content of 10ppm is processed at 20 ℃, 0.1Mpa and the liquid airspeed of 0.5h-1Reactor height to diameter ratio 10, example 1A liquid-phase dynamic dechlorination experiment was carried out under the condition that the loading amount of the dechlorinating agent was 50mL, and the chlorine content in the oil product flowing out of the dechlorination tank was measured after ten minutes of dechlorination reaction, and the results are shown in Table 1.
Example 8
The reformate with the hydrogen chloride content of 100ppm is processed at the temperature of 120 ℃, the pressure of 1Mpa and the liquid space velocity of 10h-1The results of a liquid phase dynamic dechlorination test carried out under the conditions of a reactor height/diameter ratio of 10 and a 50mL loading of the dechlorinating agent obtained in example 2 were shown in Table 1, in which the chlorine content of the oil flowing out of the dechlorination tank was measured after ten minutes of dechlorination.
Example 9
The reformate with the hydrogen chloride content of 50ppm is processed at the temperature of 40 ℃, the pressure of 0.2Mpa and the liquid space velocity of 1h-1The results of a liquid phase dynamic dechlorination test carried out under the conditions of a reactor height/diameter ratio of 10 and a 50mL loading of the dechlorinating agent obtained in example 3 were shown in Table 1, in which the chlorine content of the oil flowing out of the dechlorination tank was measured after ten minutes of dechlorination.
Example 10
The reformate with the hydrogen chloride content of 50ppm is processed at 100 ℃, 0.8Mpa and the liquid space velocity of 8h-1The results of a liquid phase dynamic dechlorination test carried out under the conditions of a reactor height/diameter ratio of 10 and a 50mL loading of the dechlorinating agent obtained in example 4 were shown in Table 1, in which the chlorine content of the oil flowing out of the dechlorination tank was measured after ten minutes of dechlorination.
Example 11
The reformate with the hydrogen chloride content of 50ppm is processed at 60 ℃, 0.4Mpa and liquid space velocity of 3h-1The results of a liquid phase dynamic dechlorination test carried out under the conditions of a reactor height/diameter ratio of 10 and a 50mL loading of the dechlorinating agent obtained in example 5 were shown in Table 1, in which the chlorine content of the oil flowing out of the dechlorination tank was measured after ten minutes of dechlorination.
Example 12
The reformate with the hydrogen chloride content of 50ppm is processed at 80 ℃, 0.6Mpa and the liquid space velocity of 5h-1The results of a liquid phase dynamic dechlorination test carried out under the conditions of a reactor height/diameter ratio of 10 and a 50mL loading of the dechlorinating agent obtained in example 6 were shown in Table 1, in which the chlorine content of the oil flowing out of the dechlorination tank was measured after ten minutes of dechlorination.
Comparative example 3
The reformate with the hydrogen chloride content of 50ppm is processed at 80 ℃, 0.6Mpa and the liquid space velocity of 5h-1A liquid phase dynamic dechlorination experiment was carried out under the conditions of a reactor height/diameter ratio of 10 and a 50mL loading of the dechlorinating agent obtained in comparative example 1, and the chlorine content in the oil product flowing out of the dechlorination tank was measured after ten minutes of dechlorination, and the results are shown in Table 1.
Comparative example 4
The reformate with the hydrogen chloride content of 50ppm is processed at 80 ℃, 0.6Mpa and the liquid space velocity of 5h-1The results of the liquid phase dynamic dechlorination test carried out under the conditions of the reactor height/diameter ratio of 10 and the loading amount of the dechlorinating agent 50mL obtained in comparative example 2 were shown in Table 1, in which the chlorine content in the oil exiting the dechlorination tank was measured after ten minutes of dechlorination.
TABLE 1 performances of dechlorinating agents obtained in examples and comparative examples
Figure BDA0001792983580000071
As can be seen from the examples and comparative examples, the dechlorinating agent prepared by the invention has larger pore volume and pore diameter, the dechlorinating efficiency of the oil liquid phase generated by reforming is more than 90 percent, and the dechlorinating precision is less than 1ppm, which is better than that of comparative examples 3 and 4. In comparative example 1, since the high-temperature roasting step of the macroporous pseudo-boehmite powder is omitted in the preparation step, the pore structure of the macroporous pseudo-boehmite powder is deformed in the subsequent kneading and extruding process, the pore volume and the pore diameter are reduced, and the dechlorination effect of the dechlorinating agent is reduced.

Claims (10)

1. The dechlorinating agent with large pore volume and large pore diameter is characterized by consisting of sodium carbonate and aluminum oxide; wherein the mass percent of the sodium carbonate is 5-30%, and the mass percent of the alumina is 70-95%; the pore volume of the dechlorinating agent is 0.5-1.5 cm3(ii)/g, the average pore diameter is 5 to 30 nm.
2. The dechlorination agent according to claim 1, wherein the pore volume of the dechlorination agent is 0.8 to 1.2cm3(ii)/g, the average pore diameter is 10 to 20 nm.
3. The dechlorination agent according to claim 1, wherein the dechlorination agent comprises 10 to 20 mass% of sodium carbonate and 80 to 90 mass% of alumina.
4. A process for the preparation of a dechlorinating agent according to any one of claims 1 to 3, comprising the steps of:
(1) the pore volume is 1.0-1.5 cm3Roasting macroporous pseudo-boehmite powder with the average pore diameter of 10-30 nm at 400-1000 ℃ to obtain alumina powder, and cooling to room temperature for later use;
(2) preparing solid sodium carbonate into a sodium carbonate aqueous solution, and cooling to room temperature for later use;
(3) uniformly mixing the alumina powder obtained in the step (1), aluminum hydroxide powder and a cellulose binder to obtain a mixed material; the pore volume and the aperture of the aluminum hydroxide powder are smaller than those of the aluminum oxide powder;
(4) and (3) dropwise adding the sodium carbonate aqueous solution obtained in the step (2) into the mixed material obtained in the step (3), kneading uniformly, and obtaining the dechlorinating agent after extrusion molding, drying and roasting.
5. The method according to claim 4, wherein the sodium carbonate aqueous solution in the step (2) has a mass concentration of 5 to 25%.
6. The preparation method according to claim 4, wherein the mass ratio of the alumina powder, the aluminum hydroxide powder and the binder in the step (3) is as follows: 100: 10-30: 1 to 3.
7. The method according to claim 4, wherein the pore volume of the aluminum hydroxide powder in the step (3) is 0.3 to 0.5cm3The average pore diameter is 3-10 nm; the cellulose binder is hydroxypropyl methylcellulose.
8. The preparation method according to claim 4, wherein the roasting temperature in the step (4) is 300 to 600 ℃, and the roasting time is 1 to 10 hours.
9. The application method of the dechlorination agent according to any one of claims 1 to 3, wherein the dechlorination agent is used for liquid-phase dechlorination of reformed oil, and the mass concentration of chlorine in the reformed oil is 10 to 100 ppm.
10. The use of claim 9, wherein the dechlorination process conditions are: the reaction temperature is 20-120 ℃; the liquid hourly space velocity is 0.5-10 h-1(ii) a The reaction pressure is 0.1-1 MPa.
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