CN115703973A - Reforming oil dechlorinating agent and preparation method and application thereof - Google Patents
Reforming oil dechlorinating agent and preparation method and application thereof Download PDFInfo
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- CN115703973A CN115703973A CN202110898437.1A CN202110898437A CN115703973A CN 115703973 A CN115703973 A CN 115703973A CN 202110898437 A CN202110898437 A CN 202110898437A CN 115703973 A CN115703973 A CN 115703973A
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- dechlorinating
- dechlorinating agent
- reformate
- sodium
- temperature
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- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000002407 reforming Methods 0.000 title description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000975 co-precipitation Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920002472 Starch Polymers 0.000 claims abstract description 11
- 239000008107 starch Substances 0.000 claims abstract description 11
- 235000019698 starch Nutrition 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 27
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000006298 dechlorination reaction Methods 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910000278 bentonite Inorganic materials 0.000 claims description 10
- 239000000440 bentonite Substances 0.000 claims description 10
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 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 description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 25
- 239000011148 porous material Substances 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 239000007791 liquid phase Substances 0.000 abstract description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract 1
- 229910001424 calcium ion Inorganic materials 0.000 abstract 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 235000010288 sodium nitrite Nutrition 0.000 description 7
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 229940092782 bentonite Drugs 0.000 description 5
- 229910000281 calcium bentonite Inorganic materials 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000280 sodium bentonite Inorganic materials 0.000 description 4
- 229940080314 sodium bentonite Drugs 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- -1 magnesium-aluminum compound Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a dechlorinating agent for reformed oil and a preparation method thereof, belonging to the technical field of dechlorinating agents and preparation methods thereof, wherein an active component is introduced when a soluble aluminum salt and a soluble alkali are subjected to coprecipitation reaction to generate pseudo-thin aluminum hydroxide, and in the whole preparation process, the activity, chlorine capacity, pore volume, specific surface area and the like of the prepared dechlorinating agent for reformed oil can be improved by introducing active carbon, calcium and magnesium ions and water-soluble starch. The dechlorinating agent for the reformed oil is suitable for removing inorganic chlorine in oil products, particularly hydrogen chloride in the reformed oil, has higher dechlorinating efficiency and dechlorinating precision in the liquid-phase dechlorinating process, and can remove the chlorine content in the reformed oil to be less than 0.5 ppm.
Description
Technical Field
The invention relates to the technical field of dechlorinating agents and preparation methods thereof, in particular to a dechlorinating agent for reformate and a preparation method and application thereof.
Background
Catalytic reforming is one of the important production processes in oil refining and petrochemical industry, and the main reaction is a process for converting naphthene and alkane into aromatic hydrocarbon or isoparaffin under the action of a bifunctional catalyst. At present, catalysts containing halogen and chlorine as acidic components are selected for catalytic reforming reactions, and in actual production operation, the chlorine content in the catalysts is gradually lost under the influence of water and the like in a reaction system. In order to ensure the activity of the catalyst and achieve the optimal water-chlorine balance, water injection and organic chloride are required to be continuously carried out. Part of water and chlorine lost in the process is accumulated in the reformate. The reformed oil is fractionated in a stabilizer (or a depentanizer), C3 and C4 components are obtained at the top of the tower, and reformed gasoline (or depentanized oil) is obtained at the bottom of the tower. The presence of small amounts of chlorine in the reformate not only affects the quality of the overhead product, but also causes corrosion of downstream stabilization systems and stripping equipment. Therefore, it is necessary to perform dechlorination of the reformed oil.
At present, a solid dechlorinating agent is generally adopted in an industrial device to remove hydrogen chloride in reformed oil, and the dechlorinating mechanism is to fix the active components in the dechlorinating agent and HCl through acid-base neutralization reaction to generate stable metal chloride so as to achieve the aim of removing HCl. 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 a binder are prepared into a dechlorinating agent by a kneading method, or the active component is loaded on a carrier by an impregnation method. For HCl in the liquid phase, the diffusion resistance is significantly greater than that of HCl molecules in the gas phase, and therefore, in addition to the active components, the specific surface area and pore volume of the dechlorination agent should be considered primarily in the preparation of the liquid phase dechlorination agent. When the existing solid dechlorinating agent is used for liquid-phase dechlorination of reformed oil, single-component alkali metal or alkaline earth metal oxide is avoided when the dechlorinating agent is used for removing HCl in liquid oil. The binary metal oxide prepared by coprecipitation method has stronger basicity, specific surface area and pore volume which are much larger than those of pure components and larger mechanical strength after being roasted. Such as: chinese patent publication No. 105542836 discloses a high-precision liquid-phase dechlorinating agent for liquid-phase dechlorination of reformate, which is composed of the following components: 5 to 20 percent of CuO, 5 to 10 percent of CaO, 4 to 8 percent 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.
The dechlorinating agent is prepared by taking the active carbon as a carrier, and the metal components are easy to lose due to weak binding force between the active carbon and the active metal components.
Chinese patent publication No. 110885699 discloses a dechlorinating agent with large pore volume and pore diameter, a preparation method and application thereof, which consists of the following components; the mass content of the sodium carbonate is 5-30%, and the mass content of the aluminum oxide is 70-95%. The preparation method comprises making the pore volume to be 1.0cm 3 G to 1.5cm 3 Roasting the pseudo-boehmite powder with the average pore diameter of 10nm to 30nm at the temperature of 400 ℃ to 1000 ℃ to obtain alumina powder; preparing solid sodium carbonate into a sodium carbonate aqueous solution, and uniformly mixing the sodium carbonate aqueous solution with the obtained alumina powder, the aluminum hydroxide powder and the cellulose binder to obtain a mixed material; and kneading the obtained mixed material uniformly, and obtaining the dechlorinating agent after extrusion molding, drying and roasting.
The dechlorinating agent takes cellulose as a binder, and alumina powder and sodium carbonate are kneaded, so that the distribution of alkaline centers is not uniform enough; when the mass content of the sodium carbonate component is more than or equal to 20 percent, the dechlorinating agent is loose and has low mechanical strength. When the mass content of the sodium carbonate component is less than or equal to 20 percent, the content of the active component is low, and the chlorine capacity of the dechlorinating agent is low. Therefore, it is a problem to be solved in the art to improve the mechanical strength, dechlorination efficiency and dechlorination accuracy of the oil phase dechlorinating agent produced by reforming.
Disclosure of Invention
The invention provides a dechlorinating agent for reformate and a preparation method thereof, which overcome the defects of the prior art, and the prepared dechlorinating agent for reformate has the advantages of uniform distribution of active centers, higher pore volume and specific surface area, and higher dechlorinating efficiency and dechlorinating precision in the liquid-phase dechlorinating process.
The invention uses acid method to prepare pseudoboehmite (that is, the pseudoboehmite is prepared by neutralization reaction of soluble aluminum salt and soluble alkali), and then Y-Al is generated by high-temperature roasting 2 O 3 In the prior art, on the basis of the prior art, active components (sodium nitrite and the like) are directly introduced in the coprecipitation step to prepare the dechlorinating agent for the reformed oil, so that the prior process step of preparing finished product alumina and then impregnating, kneading and producing the dechlorinating agent is simplified, the production cost is effectively reduced, the industrial production is easy to realize, and the environmental pollution is reduced.
One of the technical schemes of the invention is realized by the following measures: a preparation method of a dechlorinating agent for reformate comprises the following steps: firstly, carrying out coprecipitation reaction on an aluminum nitrate solution and a sodium precipitator solution at the temperature of 45-85 ℃, and obtaining a precipitate-containing solution after the coprecipitation reaction is carried out for 4-8 hours; secondly, filtering the precipitate-containing solution to obtain a filter cake (containing 53 to 57 percent of water), and drying the filter cake at the temperature of between 140 and 150 ℃ for 2 to 4 hours; thirdly, roasting the dried filter cake at 450-700 ℃ for 4-6 hours to remove the bound water to obtain alumina powder; and fourthly, uniformly mixing the alumina powder and the bentonite binder to obtain a mixed material, kneading, extruding and molding the mixed material, drying, and roasting at the temperature of 360-600 ℃ to obtain the dechlorinating agent for the reformate.
Sodium nitrate is generated in the process of coprecipitation reaction, sodium nitrate in filter cakes is decomposed into nitrous acid in the subsequent process, and sodium nitrite is uniformly distributed as an alkaline active componentIn the presence of Al 2 O 3 A surface; in the alumina powder, the content of sodium nitrite is 5 to 35 percent.
The content of sodium nitrate in the filter cake is adjusted by adjusting the concentration of reaction liquid of the coprecipitation reaction, so that the content of sodium nitrite in the alumina powder generated by roasting meets the requirement.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the sodium precipitant is one or more of sodium carbonate and sodium hydroxide, and when the sodium precipitant is a mixture of sodium carbonate and sodium hydroxide, the molar ratio of sodium carbonate to sodium hydroxide is 0.1 to 0.6.
In the step of carrying out coprecipitation reaction, 1 to 3 percent of active carbon (based on the mass of the roasted material) is added into the reaction liquid.
The activated carbon has the capacity expansion effect in the roasting process, and simultaneously, the activated carbon reacts with part of sodium nitrate to generate sodium carbonate, so that the uniformity and firmness of the alkaline component loaded on the carrier are improved.
During the kneading process of the mixed materials, water-soluble starch accounting for 3 to 10 percent of the total mass of the mixed materials is added.
3 to 10 percent of water-soluble starch is added in the kneading step, so that the extrusion performance of the alumina powder is improved, and simultaneously, the alumina powder can continuously react with part of sodium nitrite to generate sodium carbonate in the roasting process, and partial volatilization is favorable for expanding pores and expanding volume of the dechlorinating agent.
In the above-mentioned step of carrying out the coprecipitation reaction, ca is introduced into the reaction liquid 2+ Or Mg 2+ 。
In order to further improve the chlorine capacity of the dechlorinating agent and improve the mechanical strength of the dechlorinating agent, ca is introduced into a coprecipitation step of carrying out coprecipitation reaction with an aluminum nitrate solution by taking a sodium carbonate or sodium hydroxide or a mixed solution of the sodium carbonate and the sodium hydroxide as a precipitating agent 2+ Or Mg 2+ The precursor prepared by coprecipitation method has stable hydrotalcite structure, and is roasted at high temperature to obtain calcium-aluminum or magnesium-aluminum compound, na + 、Ca 2 + Or Na + 、Mg 2+ As alkaline active ingredient, are uniformly distributed. The compound not only has stronger alkaliAnd has large specific surface area and pore volume and high mechanical strength.
2+ Can be introduced by adding calcium nitrate, and when the calcium nitrate is added, the molar ratio of the calcium nitrate to the aluminum nitrate is 0.1 to 0.8; mg (magnesium) 2+ May be introduced by the addition of magnesium nitrate.
The temperature of the above coprecipitation reaction is preferably 60 to 70 ℃.
The temperature of the above third calcination is preferably 550 to 650 ℃.
The drying temperature of the fourth step is 120 ℃, the drying time is 2 hours, and the roasting temperature is preferably 400 ℃ to 500 ℃.
The addition amount of the bentonite binder is 15 to 35 percent of the sum of the mass of the alumina powder and the bentonite binder.
The bentonite binder adopts sodium-based or calcium-based bentonite.
The second technical scheme of the invention is realized by the following measures: the reformed oil dechlorinating agent is prepared by the preparation method of the reformed oil dechlorinating agent according to one technical scheme.
The third technical scheme of the invention is realized by the following measures: the application of the reforming oil dechlorinating agent in the aspect of oil product dechlorinating according to the second technical scheme.
Compared with the prior technology for preparing the dechlorinating agent by using the aluminum oxide as the carrier through kneading or dipping, the invention has the following advantages:
(1) The process steps are simplified, the production cost is effectively reduced, the industrial production is easy to realize, and the environmental pollution is reduced.
(2) The dechlorinating agent for the reformed oil takes sodium nitrite as an active center, has a stable structure, uniform distribution of the active center, higher pore volume and specific surface, and higher dechlorination efficiency and dechlorination precision in the liquid-phase dechlorination process.
(3) Introduction of Ca in the step of coprecipitation 2 + Or Mg 2+ The precursor prepared by coprecipitation method has stable hydrotalcite structure, and can be calcined at high temperature to obtain calcium-aluminum or calcium-magnesium compound, na + 、Ca 2 + 、Mg 2+ The components are used as alkaline active components and are uniformly distributed; the composite not only has stronger alkalinity, but also has large specific surface area and pore volume and larger mechanical strength.
(4) The active carbon is added in the coprecipitation step, the water-soluble starch is added in the kneading step, and the active carbon and the water-soluble starch have the functions of reaming and expanding the volume in the roasting process and simultaneously react with part of sodium nitrate and sodium nitrite to generate sodium carbonate, so that the uniformity and the firmness of the alkaline component on the carrier are improved.
The radial pressure strength of the dechlorinating agent for the reformate prepared by the invention>30N/cm, which can reach 60N/cm; chlorine capacity of 15.1-26.3 wt% and pore volume of 0.3cm 3 G to 0.69cm 3 /g。
In a word, the dechlorinating agent for the reformate is suitable for removing inorganic chlorine in oil products, particularly hydrogen chloride in the reformate, can remove the chlorine content in the reformate to be below 0.5ppm (mass ratio), and has the characteristics of high activity, large chlorine capacity, high mechanical strength, simple and stable process, strong operability and the like.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the invention is an aqueous solution of water as a solvent unless otherwise specified, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution; room temperature in the present invention generally refers to a temperature of 15 ℃ to 25 ℃, and is generally defined as 25 ℃.
The dechlorinating agent prepared in the following embodiment is the dechlorinating agent for the reformed oil of the invention. The following examples use the activated carbon: the granularity is 300 meshes, and the ml/0.1g of methylene blue is more than or equal to 11; sodium bentonite or calcium bentonite (the soreent quantity is more than or equal to 28%, the colloid value is more than or equal to 300ml/15g, the water absorption rate is more than or equal to 150%, the fineness (325 meshes) is more than or equal to 80%, and the water content is less than or equal to 11%).
The invention is further described below with reference to the following examples:
example 1
Solid aluminum nitrate (Al (NO) 3 ) 3 .9H 2 O) 376.9g of NaOH are dissolved in 1200ml of deionized water, 120g of NaOH are dissolved in 1100ml of deionized water, and 200ml of deionized water is added into a stirred three-neck flask to serve as a base solution. Stirring and carrying out parallel flow reaction at 70 ℃, finishing the addition for 1h, aging (namely coprecipitation reaction) for 6h, and carrying out suction filtration. Drying the filter cake for 2 hours at 120 ℃, roasting the filter cake for 4 hours at 650 ℃ in a muffle furnace, cooling the filter cake to obtain 58.4g of alumina powder + The content was 9.1% by mass.
35.0g of the alumina powder prepared in example 1 and 15.0g of sodium bentonite were added dropwise with deionized water and kneaded into strips (i.e., kneaded and extruded); drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
Example 2
The difference from the example 1 is that in the coprecipitation reaction process, 3.1g of 300-mesh active carbon is added into the base solution, the filter cake is dried in a muffle furnace at 120 ℃ for 2 hours, roasted at 450 ℃ for 2 hours, heated to 600 ℃ for roasting for 4 hours, and cooled to obtain 56.2g of alumina powder + The content was 9.8 mass%.
37.5g of the alumina powder prepared in the example 2 and 12.5g of sodium bentonite are added with deionized water dropwise, kneaded and extruded into strips; drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
Example 3
The difference from example 2 is that 37.5g of the prepared alumina powder, 12.5g and 4g of sodium bentonite water-soluble starch are mixed, and deionized water is dripped to knead and extrude a strip; drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
Example 4
Solid aluminum nitrate (Al (NO) 3 ) 3 .9H 2 O）(376.9g1.005mol.)，Ca(NO 3 ) 2 .4H 2 O (47.2g, 0.2mol.) was dissolved in 800ml of deionized water; 120.0g of NaOH and 21.2g of sodium carbonate are dissolved in 900ml of deionized water and added into a three-neck flask with a stirrer, and 200ml of deionized water is used as a base solution. Stirring and carrying out concurrent flow reaction at 65 ℃, aging for 6h after 1h addition, carrying out suction filtration, and washing a filter cake with 200ml of hot water at about 50 ℃. Drying the filter cake at 120 DEG CRoasting for 2 hours at 550 ℃ in a muffle furnace for 4 hours, and cooling to obtain 74.1g of calcium-aluminum powder (Ca) 2+ %8.1；Na + %4.7）。
37.5g of the calcium-aluminum powder prepared in example 4, 12.5g of calcium bentonite and 5g of water-soluble starch are mixed, deionized water is added dropwise, and the mixture is kneaded and extruded into strips; drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
Example 5
Solid aluminum nitrate (Al (NO) 3 ) 3 .9H 2 O）(376.9g1.005mol.)，Ca(NO 3 ) 2 .4H 2 O (141.6g, 0.6mol.) was dissolved in 900ml of deionized water; 120.0g of NaOH and 31.8g of sodium carbonate are dissolved in 900ml of deionized water and added into a three-neck flask with a stirrer, and 200ml of deionized water is used as a base solution. Stirring and carrying out concurrent flow reaction at 65 ℃, aging for 6h after 1h addition, carrying out suction filtration, and washing a filter cake with 300ml of hot water at about 50 ℃. The filter cake is dried for 2 hours at 120 ℃, roasted for 4 hours at 550 ℃ in a muffle furnace and cooled to obtain 82.3g of calcium-aluminum powder (Ca) 2+ %21.3；Na + %4.1）。
37.5g of the calcium-aluminum powder prepared in example 5, 12.5g of calcium bentonite and 5g of water-soluble starch are mixed, deionized water is added dropwise, and the mixture is kneaded and extruded into strips; drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
Example 6
Solid aluminum nitrate (Al (NO) 3 ) 3 .9H 2 O）(376.9g1.005mol.)，Mg(NO 3 ) 2 .6H 2 O (51.3g, 0.2mol.) was dissolved in 800ml of deionized water; 120.0g of NaOH and 21.2g of sodium carbonate are dissolved in 900ml of deionized water and added into a three-neck flask with a stirrer, and 200ml of deionized water is used as a base solution. Stirring and carrying out concurrent flow reaction at 65 ℃, aging for 6h after 1h addition, carrying out suction filtration, and washing a filter cake with 200ml of hot water at about 50 ℃. Drying the filter cake at 120 deg.C for 2 hr, calcining at 550 deg.C in muffle furnace for 4 hr, and cooling to obtain magnesium-aluminum powder 70.8g (Mg) 2+ %7.2；Na + %5.4）。
37.5g of the magnesium-aluminum powder prepared in the example 6, 12.5g of calcium bentonite and 5g of water-soluble starch are mixed, deionized water is dripped, and the mixture is kneaded and extruded into strips; drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
Example 7
Solid aluminum nitrate (Al (NO) 3 ) 3 .9H 2 O）(376.9g1.005mol.)，Mg(NO 3 ) 2 .6H 2 O (153.9g, 0.6mol.) was dissolved in 900ml deionized water; 120.0g of NaOH; sodium carbonate 21.2g was dissolved in 900ml deionised water in a stirred three-neck flask with 200ml deionised water as the base solution. Stirring and carrying out concurrent flow reaction at 65 ℃, aging for 6h after 1h addition, carrying out suction filtration, and washing a filter cake with 300ml of hot water at about 50 ℃. Drying the filter cake for 2 hours at 120 ℃, roasting the filter cake for 4 hours at 550 ℃ in a muffle furnace, and cooling to obtain 79.7g of magnesium aluminum powder (Mg) 2+ %7.2；Na + %5.1）。
37.5g of magnesium-aluminum powder prepared in example 7, 12.5g of calcium bentonite and 5g of water-soluble starch are mixed, deionized water is added dropwise, and the mixture is kneaded and extruded into strips; drying at 120 ℃ for 2h; roasting at 460 ℃ for 4h to obtain the dechlorinating agent.
The dechlorination agents obtained in examples 1 to 7 were subjected to dechlorination activity and chlorine capacity evaluation.
The method for evaluating the dechlorination activity of the liquid-phase dechlorinating agent comprises the following steps: and (2) filling a liquid-phase dechlorinating agent (namely the reformate dechlorinating agent) with the mesh of 20-40 (the invention) into an adsorption column with the inner diameter phi of 8mm, wherein the high-diameter ratio is selected to be 8 -1 (volume) into an adsorption column (top in bottom out), the chlorine content in the effluent reformate was measured and when the chlorine content was greater than 0.5ppm, breakthrough was taken and the reaction time was recorded. The dechlorination activity is good by using a long-time dechlorinating agent.
The chlorine capacity evaluation method of the liquid-phase dechlorinating agent comprises the following steps: and (2) filling the liquid-phase dechlorinating agent of 20 meshes to 40 meshes into an adsorption column with the inner diameter phi of 8mm, wherein the high-diameter ratio is 8 2 The flow is controlled by a flowmeter, and the airspeed is 1000h -1 And (4) entering an adsorption column, enabling the feed gas to pass through a bed layer from top to bottom, carrying out contact reaction with the filler, and judging that the experiment is finished when the concentration of HCl at an outlet reaches 0.5 ppm. And after the experiment is finished, taking out the dechlorinating agent in the reactor and carrying out chlorine capacity analysis. The chlorine penetration capacity (Cl%) of the dechlorinating agent means a chlorine content per unit mass of the dechlorinating agent when 0.5ppm hcl is detected in the exhaust gas of the evaluation system. The calculation formula of the penetrating chlorine capacity is as follows:
Cl%=m chlorine /m Dechlorinating agent ×100%
The pore volume, pore diameter, breakthrough time, and chlorine volume data of the dechlorinating agents prepared in examples 1 to 7 are shown in Table 1.
The data in Table 1 show that the dechlorinating agent prepared in each example has large specific surface area, pore volume and chlorine volume.
The technical characteristics form the embodiment of the invention, the embodiment has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual requirements to meet the requirements of different situations.
Claims (10)
1. A preparation method of a dechlorinating agent for reformate is characterized by comprising the following steps: firstly, carrying out coprecipitation reaction on an aluminum nitrate solution and a sodium precipitator solution at a temperature of between 45 and 85 ℃, and obtaining a precipitation-containing solution after the coprecipitation reaction is carried out for 4 to 8 hours; secondly, filtering the precipitate-containing solution to obtain a filter cake, and drying the filter cake at the temperature of between 140 and 150 ℃ for 2 to 4 hours; thirdly, roasting the dried filter cake at 450-700 ℃ for 4-6 hours to remove the bound water to obtain alumina powder; and fourthly, uniformly mixing the alumina powder and the bentonite binder to obtain a mixed material, kneading, extruding, forming, drying and roasting the mixed material at the temperature of 360-600 ℃ to obtain the dechlorinating agent for the reformed oil.
2. The process of claim 1, wherein the sodium precipitant is one or more of sodium carbonate and sodium hydroxide, and when the sodium precipitant is a mixture of sodium carbonate and sodium hydroxide, the molar ratio of sodium carbonate to sodium hydroxide is 0.1 to 0.6.
3. The method of producing a reformate dechlorinating agent according to claim 1 or 2, wherein in the step of performing the coprecipitation reaction, 1 to 3% of activated carbon is added to the reaction liquid.
4. The process for producing a reformate dechlorinating agent according to any one of claims 1 to 3, wherein the mixture is kneaded while adding water-soluble starch in an amount of 3 to 10% by mass based on the total mass of the mixture.
5. The process for producing a reformate dechlorinating agent according to any one of claims 1 to 4, wherein in the step of performing the coprecipitation reaction, ca is introduced into the reaction liquid 2+ Or Mg 2+ 。
6. The method of producing a reformate dechlorination agent according to any one of claims 1 to 5, wherein the temperature of the coprecipitation reaction is 60 ℃ to 70 ℃; or/and the temperature of the third step of roasting is 550-650 ℃.
7. The process for producing a reformate dechlorination agent according to any one of claims 1 to 6, wherein the fourth step is carried out at a drying temperature of 120 ℃ for a drying time of 2 hours; or/and the temperature of the fourth step of roasting is 400-500 ℃.
8. The process for producing a reformate dechlorinating agent according to any one of claims 1 to 7, wherein the bentonite binder is added in an amount of 15 to 35% of the sum of the mass of the alumina powder and the mass of the bentonite binder; or/and the bentonite binder adopts sodium-based or calcium-based bentonite.
9. A reformate dechlorination agent produced by the process according to any one of claims 1 to 8.
10. Use of a reformate dechlorination agent according to claim 9 for the dechlorination of an oil product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101773768A (en) * | 2010-03-16 | 2010-07-14 | 长春惠工净化工业有限公司 | Dechlorinating agent used for removing HCl from gas by dry method and preparation method thereof |
| CN102068889A (en) * | 2010-11-29 | 2011-05-25 | 长春惠工净化工业有限公司 | High-activity dechlorinating agent for fixed bed and preparation method thereof |
| CN110624382A (en) * | 2018-06-25 | 2019-12-31 | 沈阳三聚凯特催化剂有限公司 | High-temperature flue gas dechlorinating agent and preparation method thereof |
| CN110885699A (en) * | 2018-09-07 | 2020-03-17 | 中国石化扬子石油化工有限公司 | Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773768A (en) * | 2010-03-16 | 2010-07-14 | 长春惠工净化工业有限公司 | Dechlorinating agent used for removing HCl from gas by dry method and preparation method thereof |
| CN102068889A (en) * | 2010-11-29 | 2011-05-25 | 长春惠工净化工业有限公司 | High-activity dechlorinating agent for fixed bed and preparation method thereof |
| CN110624382A (en) * | 2018-06-25 | 2019-12-31 | 沈阳三聚凯特催化剂有限公司 | High-temperature flue gas dechlorinating agent and preparation method thereof |
| CN110885699A (en) * | 2018-09-07 | 2020-03-17 | 中国石化扬子石油化工有限公司 | Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof |
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