CN115041129B - Dechlorination agent for removing chloride in olefin-containing process and preparation method thereof - Google Patents

Dechlorination agent for removing chloride in olefin-containing process and preparation method thereof Download PDF

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CN115041129B
CN115041129B CN202210763929.4A CN202210763929A CN115041129B CN 115041129 B CN115041129 B CN 115041129B CN 202210763929 A CN202210763929 A CN 202210763929A CN 115041129 B CN115041129 B CN 115041129B
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hydrotalcite
olefin
dechlorinating agent
parts
containing process
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CN115041129A (en
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周立旻
卓润生
张青
施宗波
刘新生
何俊潼
刘梦梦
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Runhe Kehua Catalyst Shanghai Co ltd
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Runhe Kehua Catalyst Shanghai Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid

Abstract

The application discloses a dechlorination agent for removing chloride in an olefin-containing process and a preparation method thereof, comprising the following steps: mixing a water-soluble aluminum source, a water-soluble magnesium source and urea to obtain a reaction feed liquid; adding a surfactant into the reaction feed liquid, performing hydrothermal crystallization, washing, drying, and roasting in a nitrogen atmosphere to obtain hydrotalcite; mixing lead oxide, binder and hydrotalcite, and shaping to obtain dechlorinating agent. The dechlorinating agent takes hydrotalcite with large specific surface area as a carrier, which is beneficial to the rapid dispersion and mass transfer of active components; meanwhile, hydrotalcite is also used as an active component, and then a certain amount of lead oxide is loaded, so that the loading capacity of the active component is improved, and the dechlorination chlorine capacity is high. The antichlor has the characteristics of effectively reducing green oil, high chlorine content and high antichlor precision in the high-olefin process.

Description

Dechlorination agent for removing chloride in olefin-containing process and preparation method thereof
Technical Field
The application belongs to the technical field of petrochemical industry, and particularly relates to a dechlorination agent for removing chloride in an olefin-containing process and a preparation method thereof.
Background
In petrochemical production, many processes produce HCl impurity, which is a highly corrosive, reactive, hazardous gas that adversely affects normal production operations. For example, during catalytic reforming in a refinery, chlorine from the reforming catalyst is continually lost to the system, and organic chloride is continually injected during operation to maintain the catalyst at a certain acidity. Both chlorine lost during reforming and injected chloride are eventually present in the form of HCl in the reformed hydrogen and reformate. In addition, most of the manufacturers in China adopt an Oleflex process of UOP company, and chloride is required to be introduced in the catalyst regeneration process of the process, and the chloride finally enters the system in the form of HCl.
The HCl formed above can be combined with water in the system to generate acidic hydrochloric acid, so that the system is polluted and equipment is corroded; but also can react with ammonia in downstream equipment in the production device to generate solid ammonium chloride salt so as to block the pipeline; in addition, even small amounts of HCl can have deleterious effects on downstream catalysts. Thus, the industrial hazards of chlorine in chemical systems are mainly manifested by pollution of the system, poisoning of the catalyst, plugging of pipes and corrosion of equipment, and even the possibility of unnecessary downtime in production. So for HCl impurity in the process, in order to maintain normal operation, appropriate methods must be used to remove HCl impurity from the gas and liquid hydrocarbons.
Alkali metals are good dechlorinating agent active components that can react with HCl having acidity, causing HCl to be converted to a solid salt to be trapped. Chinese patent CN110885699B discloses a dechlorinating agent with large pore volume and pore diameter and a preparation method thereof, the dechlorinating agent is composed of sodium carbonate and alumina, the dechlorinating agent has stable pore structure and large pore volume and pore diameter, and can realize higher dechlorinating efficiency and dechlorinating precision when being used for liquid phase dechlorinating of reforming generated oil; chinese patent CN105498682a discloses a mesoporous chloride scavenger obtained by impregnating an ammonium salt solution with an active alumina powder and an alkali metal solution after mixing, and the centrally distributed high mesoporous structure improves the mass transfer rate on the basis of uniform distribution of active components, and greatly reduces the side reaction degree to olefin components.
The above patents all use Al 2 O 3 As a carrier of the adsorbent, but neglecting that alumina and organic or inorganic chlorine generate strong acid Cl-Al in the dechlorination process under the high-olefin environment 2 O 3 When the system contains a large amount of olefins and contains a part of dienes, the hydrocarbons are easy to generate polymerization reaction to generate green oil, block the pore canal of the dechlorinating agent, even accumulate a large amount to cause the blockage of a bed layer and pollute the pipeline; in addition, olefins or dienes react with HCl to form organic compoundsThe chloride cannot be effectively removed by the dechlorinating agent, so that the chloride enters downstream products, and the chloride exceeds the standard.
CN101274211 discloses a high-temperature dechlorinating agent, which comprises calcium hydroxide, calcium oxide, hydrotalcite and clay as main components, and has the characteristics of high chlorine capacity and wider application range, but the used hydrotalcite has lower specific surface area, so that active sites are fewer and only alkaline earth metal is loaded, and the dechlorinating precision is not high; CN109173979a discloses a hydrotalcite dehydrochlorination adsorbent loaded with potassium fluoride, which has good adsorption effect on acid gases such as hydrogen chloride gas, high temperature resistance, large adsorption capacity, no pollution, but not high enough removal efficiency and short service life of the adsorbent. The dechlorination agent patent disclosed above uses hydrotalcite as a carrier, but there are still problems of short service life, small specific surface area of the carrier, few active sites and the like caused by the failure to load a suitable active component.
Therefore, how to ensure Gao Lvrong and high dechlorination precision, and simultaneously reduce physical adsorption concentration of the dechlorination agent to HCl, reduce olefin polymerization and organic chloride generation in a dechlorination bed, and reduce pulverization and hardening of the dechlorination agent is an industrial technical problem.
Disclosure of Invention
In order to solve the problems, particularly the phenomenon that green oil can be generated in a high-olefin process, the application provides a antichlor for removing chloride in an olefin-containing process and a preparation method thereof.
The application is realized by the following technical scheme:
a method for preparing a dechlorinating agent for removing chloride in an olefin-containing process, which comprises the following steps:
mixing a water-soluble aluminum source, a water-soluble magnesium source and urea to obtain a reaction feed liquid; adding a surfactant into the reaction feed liquid, performing hydrothermal crystallization for 4-24 hours at 80-140 ℃, washing, drying, and roasting for 1-6 hours at 350-500 ℃ in nitrogen atmosphere to obtain hydrotalcite;
according to the mass percentage, 5 to 30 weight percent of lead oxide, 0.5 to 10 weight percent of binder and 60 to 90 weight percent of hydrotalcite are mixed and molded to obtain the dechlorinating agent.
Further, in the preferred embodiment of the present application, mg in the reaction liquid 2+ With Al 3+ The concentration ratio of (2) to (4).
Further, in a preferred embodiment of the present application, the total concentration of metal ions in the reaction liquid is 0.4 to 2.0mol/L.
Further, in a preferred embodiment of the present application, the surfactant is an anionic surfactant;
preferably, the surfactant comprises sodium dodecyl benzene sulfonate and/or polyethylene glycol;
preferably, the surfactant is polyethylene glycol PEG1000.
Further, in a preferred embodiment of the present application, the temperature during the hydrothermal crystallization is 90 to 100 ℃ and the time is 8 to 12 hours.
Further, in a preferred embodiment of the present application, the above-mentioned washing is performed until the pH of the solution is less than 8 during the washing and drying process.
Further, in a preferred embodiment of the present application, the drying temperature is 90 to 120 ℃ and the drying time is 3 to 12 hours in the washing and drying process.
Further, in the preferred embodiment of the present application, the hydrotalcite, the lead oxide and the binder are formed by dry mixing or wet mixing in the process of preparing the dechlorinating agent.
Further, in the preferred embodiment of the present application, in the dry mixing and forming process, the binder is an alkaline binder, and after mixing, the mixture is formed by granulation;
in the wet mixing forming process, hydrotalcite, lead oxide, binder and dispersion are mixed to form paste, and the paste is extruded and dried and then baked for 3 to 5 hours at 380 to 420 ℃.
The antichlor for eliminating chloride from olefin-containing process is prepared through the process.
Compared with the prior art, the application has at least the following technical effects:
the dechlorination agent for removing the chloride in the olefin-containing process provided by the application takes hydrotalcite with large specific surface area as a carrier, which is beneficial to the rapid dispersion and mass transfer of active components; meanwhile, hydrotalcite is also used as an active component, and then a certain amount of lead oxide is loaded, so that the loading capacity of the active component is improved, and the dechlorination chlorine capacity is high. The lead oxide loaded in the dechlorinating agent has higher thermal stability, so that the binder can be burnt out at higher temperature in the preparation process; insoluble lead oxide has a more reliable safety than soluble lead nitrate.
The hydrotalcite prepared by the special preparation method has a layered structure, and carbonate among layers and hydroxide on a laminate react with hydrogen chloride in solution in sequence, so that the chemical activity of the hydrotalcite is limited because chloride ions are completely absorbed into the layered structure of the hydrotalcite. The magnesium oxide component contained in the hydrotalcite can cooperate with lead oxide to form a stable active component system of the dechlorinating agent, so that the overall thermal stability of the dechlorinating agent is improved. Meanwhile, the hydrotalcite does not contain crystalline alumina, and does not generate Cl-Al with strong acidity with organic or inorganic chlorine 2 O 3 Thereby avoiding the phenomenon that the diene is polymerized to form green oil in the dechlorination process. The hydrotalcite has large specific surface area, can provide larger dispersion area for the active components, and improves the dispersion degree of the active components and the adsorption activity of the surface of the dechlorinating agent, thereby greatly improving the adsorption capacity of the dechlorinating agent.
Drawings
FIG. 1 shows XRD detection results of dechlorinating agents provided in examples 1 to 3 of the present application;
FIG. 2 is an adsorption/desorption isothermal curve of the hydrotalcite prepared in example 1 measured by a physical adsorption method;
FIG. 3 shows the results of measuring the specific surface area, pore volume and pore size distribution of hydrotalcite prepared in example 1 by physical adsorption method;
fig. 4 is SEM results of hydrotalcite prepared in example 1.
Detailed Description
Embodiments of the present application will be described in detail below with reference to the following examples, which are to be construed as merely illustrative and not limitative of the scope of the application, but are not intended to limit the scope of the application to the specific conditions set forth in the examples, either as conventional or manufacturer-suggested, nor are reagents or apparatus employed to identify manufacturers as conventional products available for commercial purchase.
The technical scheme of the application is as follows:
the preparation method of the dechlorinating agent for removing the chloride in the olefin-containing process comprises the following steps:
step S1: mixing a water-soluble aluminum source, a water-soluble magnesium source and urea to obtain a reaction feed liquid; after adding surfactant into the reaction liquid, carrying out hydrothermal crystallization for 4-24 h at 80-140 ℃, washing and drying, and roasting for 1-6 h at 350-500 ℃ in nitrogen atmosphere to obtain hydrotalcite.
Wherein the water-soluble magnesium source comprises magnesium nitrate, magnesium acetate, magnesium sulfate and the like, and the water-soluble aluminum source comprises aluminum nitrate, aluminum acetate, aluminum sulfate and the like. The water-soluble aluminum source and the water-soluble magnesium source are adopted, so that the thickness of hydrotalcite sample particles is reduced, and the specific surface area is improved. The urea is added, so that the solution is alkaline after being heated and decomposed, a required alkaline environment is provided for hydrotalcite nucleation growth, and a better removal effect is achieved.
Further, in the reaction feed liquid, the total concentration of metal ions is 0.4-2.0mol/L, mg 2+ With Al 3+ The concentration ratio of (2) to (4), i.e. [ Mg ] 2+ ]/[Al 3+ ]2 to 4; preferably, the total concentration of metal ions is 0.8-1.2mol/L, mg 2+ With Al 3+ The concentration ratio of (2) was 3. When [ Mg 2+ ]/[Al 3+ ]When the concentration ratio is too high, the specific surface area is too low, the average pore diameter is reduced, and the pore diameter distribution is widened; when the concentration ratio is too low, a stable hydrotalcite structure cannot be formed.
The surfactant is an anionic surfactant, the average granularity of grains can be obviously reduced by adding the surfactant, the anionic surfactant is favorable for adsorbing polar groups on the surface of a positively charged micelle, and a layer of compact protective film is formed on the surface of newly formed crystal nucleus particles, so that the particles are highly dispersed and are not easy to agglomerate, the granularity of the grains is reduced, and the specific surface area of the product is increased. Preferably, the surfactant comprises sodium dodecyl benzene sulfonate and/or polyethylene glycol; preferably, the surfactant is polyethylene glycol PEG1000, and the surfactant has proper polymerization degree, molecular volume and thickness of the formed adsorption layer are favorable for forming hydrotalcite with uniform particle size, small thickness and large specific surface area.
Further, the temperature in the hydrothermal crystallization process is 90-100 ℃ and the time is 8-12 h; preferably hydrothermal crystallization at 95℃for 8-12h. The hydrothermal crystallization temperature is too high, the hydrotalcite crystal structure is damaged by high temperature, and other oxide impurity phases can be formed; if the temperature is too low, the crystal phase may not be formed or other crystal phases may be formed.
Further, in the washing and drying process, the washing is performed until the pH value of the solution is less than 8, so as to wash off the residual alkali, and obtain hydrotalcite with higher purity.
Further, in the washing and drying process, the drying temperature is 90-120 ℃ and the drying time is 3-12 h; preferably, the drying temperature is 100-110 ℃ and the drying time is 6-9 h;
step S2: according to the mass percentage, 5 to 30 weight percent of lead oxide, 0.5 to 10 weight percent of binder and 60 to 90 weight percent of hydrotalcite are mixed and molded to obtain the dechlorinating agent.
Lead compounds have different valence states, and lead oxide in a high valence state has strong oxidizing property and can be reacted with HCl to be converted into lead chloride in a solid form to be deposited, so that the lead compounds can be used as effective active components of dechlorinating agents.
In the process of preparing the dechlorinating agent, hydrotalcite, lead oxide and a binder are formed by dry mixing or wet mixing.
In the dry mixing forming process, the binder is an alkaline binder, and the mixture is formed by granulating after mixing. The alkaline binder is adopted, so that the product can be molded, the strength is certain, and the alkalinity of the binder has a certain effect on removing acidic HCl.
In the wet mixing forming process, hydrotalcite, lead oxide, a binder and a dispersion liquid (such as water, ethanol and other solvents) are mixed to form paste, and the paste is extruded and dried and then baked for 3 to 5 hours at 380 to 420 ℃; preferably, the roasting temperature is 390-410 ℃ and the roasting time is 3.5-4.5 h.
The following describes specific embodiments of the present application in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the application, are not intended to limit the application.
Example 1
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the solution B while dropwise adding the ammonia water, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 110 ℃, keeping the temperature for 6 hours, quenching, filtering, washing to a pH value less than 8, and drying to obtain hydrotalcite structural powder. And roasting the powder in nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder, 25 parts of lead oxide powder and 10 parts of water glass are uniformly mixed, and the mixture is formed into short and coarse cylindrical granules with the diameter of 25mm and the height of 10-20 mm by using a granulator to prepare the dechlorinating agent DCl-A1.
Example 2
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
77 parts of magnesium nitrate hexahydrate, 37.5 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder, 25 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A2 of example 2.
Example 3
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder, 25 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A3 of example 3.
Example 4
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=2000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder, 25 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A4 of example 4.
Example 5
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
205 parts of magnesium nitrate hexahydrate, 150 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder was uniformly mixed with 25 parts of lead oxide powder and 10 parts of sodium silicate, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A5 of example 5.
Example 6
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 16 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value less than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder was uniformly mixed with 25 parts of lead oxide powder and 10 parts of sodium silicate, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A6 of example 6.
Example 7
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 180 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder was uniformly mixed with 25 parts of lead oxide powder and 10 parts of sodium silicate, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A7 of example 7.
Example 8
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
77 parts of hydrotalcite powder, 15 parts of lead oxide powder and 8 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A8 of example 8.
Example 9
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
62 parts of hydrotalcite powder, 28 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A9 of example 9.
Example 10
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
154 parts of magnesium nitrate hexahydrate, 75 parts of aluminum nitrate nonahydrate and 96 parts of urea are dissolved in 800 parts of deionized water, stirred and clarified at room temperature, and recorded as solution A; dissolving 8 parts of polyethylene glycol (Mn=1000) in 200 parts of deionized water, recording as a solution B, dropwise adding ammonia water into the solution A to adjust the pH value of the solution to 2.5, dropwise adding the ammonia water while dropwise adding the solution B, continuously stirring for 2 hours, loading the solution into a crystallization kettle for hydrothermal treatment, heating to 95 ℃, keeping the temperature for 10 hours, quenching, filtering, washing to a pH value smaller than 8, drying to obtain hydrotalcite-like structured powder, and roasting the powder in a nitrogen atmosphere at 400 ℃ for 3 hours to obtain hydrotalcite.
65 parts of hydrotalcite powder, 25 parts of lead oxide powder and 10 parts of sodium silicate are mixed into paste, the mixture is extruded into strips by using a strip extruder to obtain strips with the diameter of 2.5mm and the length of 3-6 mm, and the strips are dried and then baked for 4 hours at 400 ℃ to prepare the dechlorinating agent DCl-A10 of the example 10.
Example 11
The embodiment provides a dechlorination agent for removing chloride in an olefin-containing process, and the preparation method comprises the following steps:
65 parts of commercially available hydrotalcite powder, 25 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare the dechlorinating agent DCl-A11 of example 11.
Comparative example 1
The embodiment provides a dechlorinating agent, and the preparation method comprises the following steps:
65 parts of alumina powder, 25 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator, to prepare the dechlorinating agent DCl-B1 of comparative example 1.
Comparative example 2
The embodiment provides a dechlorinating agent, and the preparation method comprises the following steps:
65 parts of pseudo-boehmite powder, 25 parts of lead oxide powder and 10 parts of water glass were uniformly mixed, and the mixture was formed into short and coarse cylindrical pellets having a diameter of 25mm and a height of 10 to 20mm using a granulator to prepare a dechlorinating agent DCl-B2 of comparative example 2.
To illustrate the effect of the present application in providing a dechlorinating agent, the following experiments were specifically performed:
1. structural characterization:
XRD detection was performed on the dechlorinating agent prepared in examples 1 to 3, and physical adsorption and SEM analysis were performed on hydrotalcite prepared according to examples, with the following results:
FIG. 1 shows XRD results for the preparation of dechlorinating agents of examples 1-3;
FIG. 2 is an adsorption/desorption isothermal curve of the hydrotalcite prepared in example 1 measured by a physical adsorption method;
FIG. 3 shows the results of measuring the specific surface area, pore volume and pore size distribution of hydrotalcite prepared in example 1 by physical adsorption method;
fig. 4 is SEM results of hydrotalcite prepared in example 1.
From the above results, it can be seen that the process in the examples of the present application can obtain a dechlorinating agent having a hydrotalcite structure, and the hydrotalcite prepared in the examples is a layered structure, and has a large specific surface area and pore volume.
2. Performance testing
The dechlorination agents prepared in examples 1-11 and comparative examples 1-2 were subjected to dechlorination performance test on a miniature evaluation device under the following conditions: at normal temperature and normal pressure, the gas flow is 30ml/min, the loading of the dechlorinating agent is 20ml, the inlet chlorine content is 300ppm, the outlet chlorine content is analyzed by a microcoulomb instrument, and the reaction is stopped when the outlet chlorine content is less than 0.1ppm, and the experimental results are shown in table 1.
Table 1.
As can be seen from table 1, in comparison with the dechlorinating agents prepared using alumina powder or pseudo-boehmite powder as a carrier in comparative examples 1 and 2, the dechlorinating agents provided in examples 1 to 11 of the present application have higher penetrating chlorine capacity and saturated chlorine capacity than comparative examples 1 and 2, and no downstream green oil amount was detected. Therefore, the dechlorinating agent provided by the application has the characteristics of effectively reducing green oil, high chlorine capacity and high dechlorinating precision in a high-olefin process.
Meanwhile, examples 1 to 10 provide dechlorinating agents having higher penetration chlorine capacity and higher saturation chlorine capacity than example 11, compared with example 11 (preparation of dechlorinating agent using commercially available hydrotalcite powder). Therefore, compared with commercial hydrotalcite powder, the hydrotalcite powder provided by the application has the advantages that hydrotalcite is obtained by a special preparation method and is used as a carrier, so that a larger dispersing area can be provided for the active components, the dispersity of the active components and the adsorption activity of the surface of the dechlorinating agent are improved, and the adsorption capacity of the dechlorinating agent is greatly improved.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the application and is not intended to limit the scope of the application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (8)

1. A method for preparing a dechlorinating agent for removing chloride in an olefin-containing process, which is characterized by comprising the following steps:
mixing a water-soluble aluminum source, a water-soluble magnesium source and urea to obtain a reaction feed liquid; adding a surfactant into the reaction feed liquid, performing hydrothermal crystallization for 4-24 hours at 80-140 ℃, washing, drying, and roasting for 1-6 hours at 350-500 ℃ in nitrogen atmosphere to obtain hydrotalcite;
mixing and molding 5-30wt% of lead oxide, 0.5-10wt% of binder and 60-90wt% of hydrotalcite according to the total mass percentage to obtain the dechlorinating agent;
wherein, in the reaction feed liquid, the concentration ratio of Mg2+ to Al3+ is Mg2+: al3+=2 to 4:1, a step of;
the total concentration of metal ions in the reaction feed liquid is 0.4-2.0mol/L;
the temperature in the hydrothermal crystallization process is 90-100 ℃ and the time is 8-12 h;
in the washing and drying process, the drying temperature is 90-120 ℃ and the drying time is 3-12 h.
2. The method for preparing a dechlorinating agent for removing chloride in an olefin-containing process as claimed in claim 1, wherein the surfactant is an anionic surfactant;
3. the method for preparing a dechlorinating agent for removing chloride in an olefin-containing process according to claim 1, wherein the surfactant comprises sodium dodecylbenzene sulfonate and/or polyethylene glycol.
4. The method for preparing a dechlorinating agent for removing chloride from an olefin-containing process as claimed in claim 1, wherein the surfactant is polyethylene glycol PEG1000.
5. The method for preparing a dechlorinating agent for removing chlorides from an olefin-containing process according to claim 1, wherein the washing and drying process is performed until the pH value of the solution is less than 8.
6. The method for preparing a dechlorinating agent for removing chloride in an olefin-containing process as claimed in claim 1, wherein the hydrotalcite, lead oxide and binder are formed by dry mixing or wet mixing during the preparation of the dechlorinating agent.
7. The method for preparing a dechlorinating agent for removing chloride from an olefin-containing process as claimed in claim 6, wherein in the dry mixing and forming process, the binder is an alkaline binder, and the mixture is granulated and formed.
8. A dechlorinating agent for removing chlorides in an olefin-containing process, which is produced by the production method according to any one of claims 1 to 7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010111849A1 (en) * 2009-04-02 2010-10-07 北京化工大学 Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof
CN104338524A (en) * 2013-08-06 2015-02-11 中国石油大学(北京) Lubricating oil basic oil raw material esterification deacidification catalyst and application thereof
CN106861386A (en) * 2017-01-22 2017-06-20 万华化学集团股份有限公司 A kind of antichlor and preparation method thereof
CN113231033A (en) * 2021-04-15 2021-08-10 东南大学 Preparation method of organic acid radical ion column-supported hydrotalcite-like adsorbent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010111849A1 (en) * 2009-04-02 2010-10-07 北京化工大学 Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof
CN104338524A (en) * 2013-08-06 2015-02-11 中国石油大学(北京) Lubricating oil basic oil raw material esterification deacidification catalyst and application thereof
CN106861386A (en) * 2017-01-22 2017-06-20 万华化学集团股份有限公司 A kind of antichlor and preparation method thereof
CN113231033A (en) * 2021-04-15 2021-08-10 东南大学 Preparation method of organic acid radical ion column-supported hydrotalcite-like adsorbent

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