CN116286078A - Liquid-phase dechlorinating agent and preparation method thereof - Google Patents
Liquid-phase dechlorinating agent and preparation method thereof Download PDFInfo
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- CN116286078A CN116286078A CN202310292229.6A CN202310292229A CN116286078A CN 116286078 A CN116286078 A CN 116286078A CN 202310292229 A CN202310292229 A CN 202310292229A CN 116286078 A CN116286078 A CN 116286078A
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- dechlorinating agent
- liquid
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- zinc
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- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 79
- 239000007791 liquid phase Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 80
- 239000011148 porous material Substances 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000969 carrier Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 238000006298 dechlorination reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 229960000892 attapulgite Drugs 0.000 claims description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- -1 carbonate compound Chemical class 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000460 chlorine Substances 0.000 abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 abstract description 26
- 238000005096 rolling process Methods 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- 239000002689 soil Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001833 catalytic reforming Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 belongs to the technical field of petrochemical industry, and particularly provides a liquid-phase dechlorinating agent and a preparation method thereof, wherein the raw materials of the dechlorinating agent comprise, by mass, 12% -20% of sodium-containing active compounds, 40% -60% of zinc-containing active compounds, 10% -20% of clay carriers and 5% -25% of auxiliary agents. The pore distribution of the dechlorinating agent is optimally regulated through heating and decomposing active material precursors to form pores and porous carriers such as alumina, molecular sieve, aluminosilicate clay and the like, and a reasonable pore distribution structure plays a synergistic effect through interaction of highly uniformly dispersed active components, so that the dechlorinating precision and chlorine capacity of the dechlorinating agent are greatly improved; the invention is formed in a rolling ball mode, has simple forming mode and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a liquid-phase dechlorinating agent for removing chloride ions in catalytic generated oil in a catalytic reforming device and a preparation method thereof.
Background
The continuous catalytic reforming process is an important component of modern oil refining processes, mainly producing high octane gasoline and hydrogen rich. In the reforming reaction process, the reforming catalyst is subjected to reaction and regeneration circulation, chlorine is injected in the regeneration process for chloridizing renewal so as to keep the water chlorine balance of the catalyst, and part of chlorine is dissolved into the generated oil in the process. Along with the extension of the operation period of the reforming catalyst, the chlorine holding capacity of the reforming catalyst is gradually reduced, the chlorine supplementing outside the system is increased, the chlorine content in the reformed oil is also increased, and the subsequent corrosion of the device and the accumulation of the chlorine content in the solvent of the extraction system can be caused. In order to eliminate the influence of the chlorides, a solid dechlorination method is adopted to remove the hydrogen chloride in the generated oil, so that the method is a very effective method.
Various liquid-phase dechlorinating agents are developed by domestic and foreign agent companies and applied to catalytic reforming devices, such as PCL-100, PCL-200 liquid-phase dechlorinating agents developed by UOP company, D267A liquid-phase dechlorinating agents of Zhuang Xinmo Feng company, dan Keyuan RCL-1 dechlorinating agents, shanghai friendly Tai YH-7250 molecular sieve dechlorinating agents and the like.
With the continuous expansion of the scale of catalytic reforming in China, the market competition of the liquid-phase dechlorinating agent is more and more vigorous, and the dechlorinating precision requirement of the liquid-phase dechlorinating agent is higher and higher. In summary, how to optimize the formulation and the preparation process of the liquid-phase dechlorinating agent, improve the chlorine capacity and the dechlorinating effect, so that the performance of the liquid-phase dechlorinating agent is comparable to that of the high-performance liquid-phase dechlorinating agent in domestic and foreign markets, and the technical problem still needs to be solved.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of small chlorine capacity of the dechlorinating agent in the prior art, thereby providing a liquid-phase dechlorinating agent with high chlorine capacity and a preparation method thereof.
The invention provides a liquid-phase dechlorinating agent, which comprises, by mass, 12% -20% of sodium-containing active compounds, 40% -60% of zinc-containing active compounds, 10% -20% of clay carriers and 5% -25% of auxiliary agents.
Further, the zinc-containing active compound is selected from at least one of zinc oxide, basic zinc carbonate, zinc carbonate or zinc hydroxide.
Further, the active compound is at least one selected from sodium carbonate, sodium bicarbonate and sodium hydroxide.
Further, the dechlorinating agent also comprises 0-5% of an oxide, hydroxide or carbonate compound of at least one of Cu, ca, fe, K and Mn.
Further, the auxiliary agent is the specific surface area150-400m 2 Per gram, pore volume of 0.2-1.0cm 3 Activated alumina powder/g and specific surface area of 400-700m 2 Per g, pore volume of 0.2-0.4cm 3 One or more of 13X molecular sieve powder/g.
Further, the clay carrier includes at least one of bentonite, diatomaceous earth, and attapulgite.
The invention also provides a preparation method of the liquid-phase dechlorinating agent, which is characterized by comprising the following steps: mixing zinc-containing active compound, sodium-containing active compound, clay carrier and auxiliary agent, forming, drying and roasting to obtain the dechlorination agent.
Further, the roasting temperature is 400-650 ℃ and the roasting time is 2-6h.
Still further, the temperature of the firing is preferably 450 ℃ to 530 ℃.
Further, the forming is formed by spraying silica sol aqueous solution to form rolling balls, and the particle size of the formed particles is 2-5mm.
The technical scheme of the invention has the following advantages:
1. the liquid-phase dechlorinating agent provided by the invention adopts the zinc-containing active compound and the sodium-containing active compound as active components, the active components can play a synergistic effect to facilitate the improvement of dechlorinating activity, and the sodium salt of the active component does not show a diffraction front in an XRD spectrogram, so that the particles are very small, and the high dispersion in the dechlorinating agent is achieved; the pore canal of the dechlorinating agent is optimized through the adjustment of the auxiliary agent, and the sodium-containing active compound and the zinc-containing active compound are mutually matched to play a synergistic effect under the specific content, so that the dechlorinating activity of the dechlorinating agent is greatly improved; through reasonable distribution among the zinc-containing active compound, the sodium-containing active compound, the clay carrier and the auxiliary agent, the active components are uniformly distributed and can be contacted with chlorine to the greatest extent, and the prepared dechlorinating agent has high chlorine capacity and good dechlorinating effect.
2. The dechlorination agent provided by the invention has the advantages of simple preparation method, moderate strength and good water resistance, and is suitable for industrial production.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge. Silica sol used in the present invention was purchased from Shen Yangxin photostripper plant; attapulgite, available from Ming Guangshi Li Yuan mineral Co., ltd; peng Runzhen, purchased from Weifang Yong Bentonite Limited; diatomaceous earth, available from Jilin Yuantong mining Co., ltd; tianfen from Fushun chemical Co., ltd; methylcellulose, available from wheatstone fine chemical company in north of western security; zeolite X, available from the university of south opening catalyst plant.
Example 1
The embodiment provides a dechlorinating agent, which specifically comprises the following components: 50g of ZnO and 50g of Zn are taken 2 (OH) 2 CO 3 3g，Na 2 CO 3 15g of NaOH 2g of 13X molecular sieve powder (ratio Table 470 m) 2 Per g, pore volume 0.22cm 3 10 g), mixing 15g of attapulgite, spraying 23.8mL of silica sol aqueous solution with mass and volume percentage of 28% (g/100 mL), forming by rolling balls, and drying at 120 ℃ for 4 hours, wherein the particle size of the particles is 3-4 mm; and then roasting for 4 hours at 480 ℃ to obtain the dechlorinating agent.
Example 2
The embodiment provides a dechlorinating agent, which specifically comprises the following components: 50g of ZnO and 50g of Zn are taken 2 (OH) 2 CO 3 3g，Na 2 CO 3 15g, naOH 0.7g, activated alumina powder (specific surface 300m 2 Per g, pore volume 0.7cm 3 10g of activated alumina powder (ratio Table 170 m) 2 Per g, pore volume 0.2cm 3 5 g/g) and 15g of Peng-run soil, spraying 24.7mL of silica sol aqueous solution with mass volume percentage of 28% (g/100 mL) to form a ball, drying at 120 ℃ for 4h, and thenRoasting for 4 hours at 480 ℃ to obtain the dechlorinating agent.
Example 3
The embodiment provides a dechlorinating agent, which specifically comprises the following components: 50g of ZnO and ZnCO are taken 3 3g，NaOH 0.5g，Na 2 CO 3 20g of activated alumina powder (ratio Table 170m 2 Per g, pore volume 0.2cm 3 10 g/g), 13X molecular sieve powder (ratio Table 470m 2 Per g, pore volume 0.22cm 3 15 g/g), and 15g of attapulgite clay are mixed, 25.9mL of silica sol aqueous solution with the mass volume percentage of 28 percent (g/100 mL) is sprayed for rolling ball forming, the particle size of the particles is 3-4mm, the particles are dried for 4 hours at 120 ℃, and then the particles are baked for 4 hours at 480 ℃ to obtain the dechlorinating agent.
Example 4
The embodiment provides a dechlorinating agent, which specifically comprises the following components: 50g of ZnO and 50g of Zn are taken 2 (OH) 2 CO 3 5g，CuO0.5g，Na 2 CO 3 16g of activated alumina powder (ratio Table 300m 2 Per g, pore volume 0.42cm 3 10g of activated alumina powder (ratio Table 370 m) 2 Per g, pore volume 0.7cm 3 5 g/g), and 15g of Peng-run soil are mixed, 25.4mL of silica sol aqueous solution with mass volume percentage of 28% (g/100 mL) is sprayed for ball forming, the particle size of the particles is 3-4mm, the particles are dried for 4 hours at 120 ℃, and then the particles are baked for 4 hours at 480 ℃ to obtain the dechlorination agent.
Example 5
The embodiment provides a dechlorinating agent, which specifically comprises the following components: 40g of ZnO, zn (OH) is taken 2 :5g，ZnCO 3 ，3g，Na 2 CO 3 20g，Cu(NO 3 ) 2 1g of activated alumina powder (ratio Table 370m 2 Per g, pore volume 0.7cm 3 10 g/g), 13X molecular sieves (ratio of 660m 2 Per g, pore volume 0.32cm 3 5 g/g), activated alumina powder (ratio Table 170m 2 Per g, pore volume 0.22cm 3 And/g) 10g, 15g of diatomite is mixed, 27.3mL of silica sol aqueous solution with mass volume percentage of 28% (g/100 mL) is sprayed for ball forming, the particle size of the particles is 3-4mm, the particles are dried for 4h at 120 ℃, and then the particles are roasted for 4h at 480 ℃ to obtain the dechlorinating agent.
Example 6
The embodiment provides a dechlorinating agent, which specifically comprises the following components: 45g of ZnO and 45g of Zn are taken 2 (OH) 2 CO 3 5g，Na 2 CO 3 15g of activated alumina powder (ratio Table 170m 2 Per g, pore volume 0.2cm 3 10g of activated alumina powder (ratio Table 370 m) 2 Per g, pore volume 0.7cm 3 5 g/g), and 15g of Peng-run soil, and then spraying 23.8mL of a silica sol aqueous solution with the mass volume percentage of 28% (g/100 mL) to form a rolling ball, wherein the particle size of the rolling ball is 3-4mm, drying the rolling ball at 120 ℃ for 4 hours, and roasting the rolling ball at 480 ℃ for 4 hours to obtain the dechlorination agent.
Example 7
This example provides a dechlorinating agent substantially identical to example 4, except that: the roasting temperature is changed to 550 ℃, and the dechlorinating agent is prepared.
Example 8
The embodiment provides a dechlorinating agent, which is specifically as follows: zn is taken out 2 (OH) 2 CO 3 75g，CuO 0.5g，Na 2 CO 3 16g of activated alumina powder (ratio Table 300m 2 Per g, pore volume 0.42cm 3 10g of activated alumina powder (ratio Table 370 m) 2 Per g, pore volume 0.7cm 3 5 g/g), and 15g of Peng-run soil, spraying 30.3mL of silica sol aqueous solution with mass and volume percentage of 28% (g/100 mL), forming a rolling ball, drying at 120 ℃ for 4 hours, and roasting at 480 ℃ for 4 hours to obtain the dechlorination agent.
Example 9
The embodiment provides a dechlorinating agent, which is specifically as follows: znO 53.5g,CuO 0.5g,Na is taken 2 CO 3 16g of activated alumina powder (ratio Table 300m 2 Per g, pore volume 0.42cm 3 10g of activated alumina powder (ratio Table 370 m) 2 Per g, pore volume 0.7cm 3 5 g/g), and 15g of Peng-run soil, spraying 24.9mL of a silica sol aqueous solution with the mass volume percentage of 28% (g/100 mL), forming a rolling ball, drying the rolling ball at the temperature of 120 ℃ for 4 hours, and roasting the rolling ball at the temperature of 480 ℃ for 4 hours to obtain the dechlorinating agent.
Comparative example 1
The comparative example provides a dechlorinating agent, which is specifically: 50g of ZnO and 50g of Zn are taken 2 (OH) 2 CO 3 3g，Na 2 CO 3 10g，MnCO 3 2g of activated alumina powder (ratio Table 370m 2 Per g, pore volume 0.7cm 3 Per g) 10g, attapulgite15g of soil is mixed, 24.9mL of silica sol aqueous solution with mass volume percentage of 28% (g/100 mL) is sprayed for rolling ball forming, the particle size of the particles is 3-4mm, the particles are dried for 4 hours at 120 ℃, and then the particles are baked for 4 hours at 550 ℃ to obtain the dechlorinating agent.
Comparative example 2
The comparative example provides a dechlorinating agent, which is specifically: 40g of ZnO, zn (OH) is taken 2 5g，ZnCO 3 3g，Na 2 CO 3 10g, cuO 1g, activated alumina powder (ratio 370m 2 g, pore volume 0.7cm 3 10 g/g), 15g of attapulgite is mixed, 22.5mL of silica sol aqueous solution with the mass volume percentage of 28 percent (g/100 mL) is sprayed for rolling ball forming, the particle size of the particles is 3-4mm, the particles are dried for 4 hours at 120 ℃, and then the particles are baked for 4 hours at 480 ℃ to obtain the dechlorinating agent.
Comparative example 3
The comparative example provides a dechlorinating agent, which is specifically: 50g of ZnO and 50g of Zn are taken 2 (OH) 2 CO 3 3g，Na 2 CO 3 12g，Cu(NO 3 ) 2 1g,13X molecular sieve powder (ratio Table 470m 2 Per g, pore volume 0.22cm 3 10g of activated alumina powder (ratio Table 370 m) 2 Per g, pore volume 0.7cm 3 5 g/g), and 15g of attapulgite are mixed, 21.0mL of silica sol aqueous solution with mass volume percentage of 28% (g/100 mL) is sprayed for ball forming, the particle size of the particles is 3-4mm, the particles are dried for 4 hours at 120 ℃, and then the particles are baked for 4 hours at 480 ℃ to obtain the dechlorinating agent.
Comparative example 4
The comparative example provides a dechlorinating agent, specifically referring to the method of CN105542836A example 3, a modified activated carbon-based dechlorinating agent is prepared, and the components comprise 12.5wt% of CuO,10wt% of CaO,4wt% of KOH and the balance of modified activated carbon; in the preparation process, firstly, the activated carbon is modified, then, copper acetate-calcium acetate solution containing ethylenediamine tetraacetic acid is used for impregnating the modified activated carbon, after the impregnation is finished, the solid phase is collected and baked for 6 hours under the anaerobic condition at 500 ℃, finally, the baked product of the last step is placed in 25wt% KOH aqueous solution again for 2 hours, and then, the solid phase is collected and dried for 7 hours at 100 ℃ to obtain the dechlorination agent. See CN105542836a example 3 for detailed steps.
Comparative example 5
This comparative example provides a take-offChlorine reagent, in particular according to the method of example 1 of CN104560126A, 30g of macroporous alumina (BET: 370m 2 /g, pore volume: 0.8 ml/g), 30g of mesoporous alumina (BET: 180m 2 /g, pore volume: 0.42 ml/g), 30g of small-pore alumina (BET: 270m 2 /g, pore volume: 0.20 ml/g), zeolite X (BET: 500m 2 /g, pore volume: 0.52 mL/g), 30g of calcium hydroxide, 40g of zinc oxide, 5g Tianfen and 5g of methyl cellulose, then adding 110mL of nitric acid with mass concentration of 8%, uniformly mixing, extruding to form strips, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours to obtain the dechlorinating agent.
Experimental example 1 sample chlorine Capacity
The test results of removing HCL in the reformed oil by the dechlorinating agent prepared in each example and comparative example are specifically as follows: the generated oil with the chlorine content of about 100mg/L and the water content of 50ppm is at normal pressure and the liquid airspeed is 16h -1 The reaction temperature is 25 ℃, and the height-diameter ratio is 3.2:1, carrying out a dechlorination agent fixed bed dechlorination experiment, determining the content of outlet chlorine by using a jena company multi5500 chlorine analyzer, ending the experiment when the content of chlorine in the outlet oil is more than 0.5mg/L, taking out a dechlorination agent waste agent, carrying out the chlorine content determination of the waste agent by using a coulomb analyzer, comparing and evaluating the chlorine content of a sample, and calculating the chlorine content by using a formula: chlorine capacity= (mass content of chlorine in dechlorinating agent/total mass of dechlorinating agent after use) = 100%, the results are as follows:
as is clear from the above table, compared with the liquid-phase dechlorinating agent prepared in comparative examples 1-5, the content of the sodium-containing active compound in the liquid-phase dechlorinating agent prepared in examples 1-9 of the invention is 12-20%, sodium salt can be rapidly combined with chlorine to form sodium chloride to play a dechlorinating effect, zinc salt plays a role in finely removing a small part of chlorine, two active components form a reasonable proportion, synergistic components are exerted to improve dechlorinating activity, and ZnO is typicalIs a component of fine dechlorination, zn 2 (OH) 2 CO 3 In the roasting process, zinc oxide can be pyrolyzed and converted to release gas, and a pore-forming function is provided in the dechlorinating agent, so that the optimal pore channel distribution is adjusted and formed to improve the dechlorinating effect; compared with the liquid-phase dechlorinating agent prepared in comparative examples 6 and 7, the liquid-phase dechlorinating agent prepared in the embodiment of the invention not only contains sodium active compound and zinc active compound, but also has the advantages of adjusting the pore canal structure by using alumina, molecular sieve and precursors of different active materials, so that the optimal distribution of dechlorinating effect is achieved, and the chlorine capacity is obviously improved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The liquid-phase dechlorinating agent is characterized by comprising, by mass, 12% -20% of sodium-containing active compounds, 40% -60% of zinc-containing active compounds, 10% -20% of clay carriers and 5% -25% of auxiliary agents.
2. The liquid-phase dechlorinating agent according to claim 1, wherein the zinc-containing active compound is at least one selected from zinc oxide, basic zinc carbonate, zinc carbonate or zinc hydroxide.
3. The liquid-phase dechlorinating agent according to claim 1, wherein the active compound is at least one selected from sodium carbonate, sodium bicarbonate and sodium hydroxide.
4. A liquid phase dechlorinating agent according to any one of claims 1-3, characterised in that it further comprises 0% -5% of an oxide, hydroxide or carbonate compound of at least one of Cu, ca, fe, K and Mn.
5. The liquid-phase dechlorinating agent as claimed in claim 1, wherein the auxiliary agent has a specific surface area of 150-400m 2 Per gram, pore volume of 0.2-1.0cm 3 Activated alumina powder/g and specific surface area of 400-700m 2 Per g, pore volume of 0.2-0.4cm 3 One or more of 13X molecular sieve powder/g.
6. The liquid phase dechlorinating agent according to claim 1, wherein the clay carrier comprises at least one of bentonite, diatomaceous earth and attapulgite.
7. The method for preparing a liquid-phase dechlorinating agent as claimed in any one of claims 1 to 6, characterized by comprising the steps of: mixing zinc-containing active compound, sodium-containing active compound, clay carrier and auxiliary agent, forming, drying and roasting to obtain the dechlorination agent.
8. The method for preparing a liquid-phase dechlorinating agent as claimed in claim 7, wherein the roasting temperature is 400-650 ℃ and the time is 2-6h.
9. The method for preparing a liquid-phase dechlorinating agent as claimed in claim 7 or 8, characterized in that the roasting temperature is preferably 450-530 ℃.
10. The method for preparing a liquid-phase dechlorinating agent as claimed in claim 7, wherein the shaping is a spray-silica sol aqueous solution ball shaping, and the particle size of the shaped particles is 2-5mm.
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