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CN-121495546-B - Heat storage material and preparation method and application thereof

CN121495546BCN 121495546 BCN121495546 BCN 121495546BCN-121495546-B

Abstract

The invention belongs to the technical field of low-carbon dehydrogenation aids, and particularly relates to a heat storage material, a preparation method and application thereof. The heat storage material comprises, by mass, 70% -92% of a heat storage main component, 1% -8% of alpha-Al 2 O 3 5%-25%、Sb 2 O 3 and 0.5% -5% of SiO 2 , wherein the heat storage main component comprises at least three of MgO, caO, niO, zrO 2 and CeO 2 . According to the invention, through the synergistic effect of the MgO-CaO-NiO-ZrO 2 /CeO 2 multi-element heat storage system and the combination of Sb 2 O 3 electronic modification and SiO 2 structural reinforcement, the heat storage material with high side pressure strength and excellent thermal shock stability is prepared. The material can effectively reduce bed temperature drop, improve propylene selectivity and show good long-term running stability.

Inventors

  • DENG ZHONGHUA
  • CHEN LING

Assignees

  • 大连康塔莱精细化工研究有限公司

Dates

Publication Date
20260512
Application Date
20260112

Claims (8)

  1. 1. The heat storage material is characterized by comprising, by mass, 70% -92% of a heat storage main component, 1% -8% of alpha-Al 2 O 3 5%-25%、Sb 2 O 3 and 0.5% -5% of SiO 2 , wherein the heat storage main component comprises at least three of MgO, caO, niO, zrO 2 and CeO 2 , and at least comprises MgO, caO and NiO; wherein the mass ratio of MgO, caO and NiO in the main heat storage component is (4-6) (1.5-3) 1; The preparation method of the heat storage material comprises the following steps: (1) Mixing a precursor of a main heat storage component, alpha-Al 2 O 3 、Sb 2 O 3 and SiO 2 , adding a binder and water, and mixing to obtain a uniform plastic body; (2) Extruding plastic body to form strips, drying and granulating to obtain strip material; (3) Roasting the strip-shaped object to obtain the heat storage material; the roasting condition in the step (3) is that the temperature is raised to 1300-1500 ℃ at the speed of 1-3 ℃ per minute, and the temperature is kept for 2-4 hours.
  2. 2. The heat storage material according to claim 1, wherein the heat storage main component is composed of MgO, caO, niO and ZrO 2 , and the mass ratio of MgO, caO, niO and ZrO 2 is (4-6): 1.5-3): 1 (1-2).
  3. 3. The heat storage material according to claim 1, wherein the heat storage main component consists of MgO, caO, niO and CeO 2 , and the mass ratio of MgO, caO, niO to CeO 2 is (3.5-6): (1.5-3.5): 1 (1-3.5).
  4. 4. The heat storage material according to any one of claims 1 to 3, wherein the heat storage material has a property parameter including a cylindrical bar having a diameter of 2 to 4mm and a length of 5 to 12mm, and a side pressure strength of not less than 400N/cm.
  5. 5. A method for producing the heat storage material according to any one of claims 1 to 4, comprising the steps of: (1) Mixing a precursor of a main heat storage component, alpha-Al 2 O 3 、Sb 2 O 3 and SiO 2 , adding a binder and water, and mixing to obtain a uniform plastic body; (2) Extruding plastic body to form strips, drying and granulating to obtain strip material; (3) Roasting the strip-shaped object to obtain the heat storage material; the roasting condition in the step (3) is that the temperature is raised to 1300-1500 ℃ at the speed of 1-3 ℃ per minute, and the temperature is kept for 2-4 hours.
  6. 6. The preparation method according to claim 5, wherein the binder in the step (1) is at least one selected from the group consisting of polyvinyl alcohol, alumina sol and methylcellulose, the binder is added in an amount of 2-8% of the total mass of the raw material powder, and the water is added in an amount of 20-35% of the total mass of the raw material powder.
  7. 7. The method according to claim 5, wherein the precursor of the heat storage main component in the step (1) is selected from at least three of Mg (OH) 2 、CaCO 3 、Ni(NO 3 ) 2 ·6H 2 O、Zr(OH) 4 and Ce (NO 3 ) 3 ·6H 2 O), and the drying temperature in the step (2) is 100-180 ℃ and the drying time is 2-10h.
  8. 8. Use of the thermal storage material according to any one of claims 1 to 4 in a reaction for producing olefins by dehydrogenation of alkanes.

Description

Heat storage material and preparation method and application thereof Technical Field The invention belongs to the technical field of low-carbon dehydrogenation aids, and particularly relates to a heat storage material, a preparation method and application thereof. Background Thermal storage materials are common thermal storage components in thermal storage devices, and generally include metallic thermal storage materials, ceramic thermal storage materials, and phase change thermal storage materials. Alkane dehydrogenation reactions are typically endothermic and the overall process may be run as an adiabatic cyclic process. On one hand, in the propane dehydrogenation process, the catalyst bed often has the problem of uneven axial and radial temperature distribution, so that the local reaction efficiency is reduced, the catalyst is easy to deactivate, and on the other hand, the objectively existing bed pressure drop is uneven, and in the reaction process, the uneven temperature drop at different positions of the bed is caused by bias flow, so that the uneven reaction is caused, and the service life of the catalyst and the propylene product yield are seriously influenced. In the traditional process, in order to maintain the reaction temperature, a large amount of heat storage materials such as inert alumina are often doped in the catalyst bed, so that the actual filling volume of the catalyst only accounts for 50% -70% of the bed, the space utilization rate of the reactor is low, the equipment volume is large, and the energy consumption is high. The Chinese patent application CN117925196A discloses a heat balance material used in the process of dehydrogenating low-carbon alkane, a preparation method and application thereof, and relates to the technical field of dehydrogenating low-carbon alkane, wherein the heat balance material comprises a carrier, a main active component and an auxiliary active component; the main active component comprises Cu, and the auxiliary active component comprises Ca and at least one element in IVA group. The main active component in the heat balance material can be distributed more uniformly by adding one element in IVA group in the auxiliary active component, and the sintering caused by repeated high-temperature roasting of the main active component can be reduced by mixing and kneading, first high-temperature roasting, dipping and then second high-temperature roasting. But the preparation of the composite material needs multiple times of dipping and roasting, the process is complex, and the active components are easy to sinter. The Chinese patent application CN112812751A discloses a heat storage material for propylene preparation process by catalytic dehydrogenation of propane and a preparation method thereof, wherein the heat storage material is a supported composite metal oxide xMaOb/carrier, wherein one or more of M= Ba, mg, mn, zr, ca, ce, bi, cu, co, mo, fe, ni, na, nb, sb, a=1-3, b=1-3 and x is the supported amount of the composite metal oxide, and the value of the supported heat storage material is 10-30wt%. Although the heat storage material can release heat in the regeneration stage, the material form control is not involved, and the traditional powder or granular material is easy to cause pressure drop increase and abrasion, and the temperature balance of a bed layer is insufficient. Chinese patent application CN107074683a discloses a CuO heat release material that releases heat by reacting CO with CuO to form Cu and CO 2. However, the method introduces components such as CO and CO 2 while introducing heat, so that the partial pressure of the reaction gas is reduced, and the reaction conversion rate is affected. Therefore, the development of the heat storage material with higher heat storage density, better heat stability and simple preparation is of great significance for promoting the progress of the propane dehydrogenation process. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a heat storage material used in a propane dehydrogenation process, and a preparation method and application thereof. In order to achieve the above purpose of the present invention, the present invention adopts the following specific technical scheme: The heat storage material comprises, by mass, 70% -92% of a heat storage main component, 1% -8% of alpha-Al 2O35%-25%、Sb2O3% and 0.5% -5% of SiO 2, wherein the heat storage main component comprises at least three of MgO, caO, niO, zrO 2 and CeO 2. Preferably, the mass ratio of MgO, caO and NiO in the main heat storage component is (4-6): (1.5-3): 1. Further preferably, the heat storage main component consists of MgO, caO, niO and ZrO 2, and the mass ratio of MgO, caO, niO to ZrO 2 is (4-6): (1.5-3): 1 (1-2). Further preferably, the heat storage main component consists of MgO, caO, niO and CeO 2, and the mass ratio of MgO, caO, niO to CeO 2 is (3.5-6): (1.5-3.5): 1 (1-3.5). Preferably, the thermal storage mate