CN116477586A - Impurity removing method for dichloro sulfonyl imide - Google Patents
Impurity removing method for dichloro sulfonyl imide Download PDFInfo
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- CN116477586A CN116477586A CN202310000494.2A CN202310000494A CN116477586A CN 116477586 A CN116477586 A CN 116477586A CN 202310000494 A CN202310000494 A CN 202310000494A CN 116477586 A CN116477586 A CN 116477586A
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- molecular sieve
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- 239000012535 impurity Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 88
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000003463 adsorbent Substances 0.000 claims abstract description 88
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- 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 48
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 46
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 34
- 239000010955 niobium Substances 0.000 claims abstract description 34
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 30
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 13
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000012043 crude product Substances 0.000 claims description 25
- -1 niobium modified MCM-41 Chemical class 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000013638 trimer Substances 0.000 abstract description 11
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 abstract 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 52
- 238000004090 dissolution Methods 0.000 description 30
- 239000002994 raw material Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- GBFOVGYSKHACRD-UHFFFAOYSA-N dichloro-imino-oxo-lambda6-sulfane Chemical compound ClS(Cl)(=N)=O GBFOVGYSKHACRD-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for removing impurities from dichloro sulfonyl imide, which comprises the following steps: the method solves the problem that impurities are difficult to remove in the process of preparing the crude difluoro sulfimide by a sulfoxide chloride method, and the method is to adsorb the impurities in the crude difluoro chlorosulfonimide prepared by the sulfoxide chloride method by taking a mesoporous molecular sieve modified by tantalum and/or niobium as an adsorbent. According to the invention, the tantalum and niobium modified mesoporous molecular sieve is used as an adsorbent, so that heavy component impurities such as chlorosulfonic acid, dichloro dimer, dichloro trimer tar and the like in the coarse product of the dichloro sulfimide prepared by a thionyl chloride method can be rapidly adsorbed, the quality of the removed product can be obviously improved, and the influence on subsequent reactions is reduced.
Description
Technical Field
The invention belongs to the technical field of electrolyte, and particularly relates to a method for removing impurities from dichloro-sulfonyl-imide.
Background
At present, electric power is a medium-current whetstone of renewable resources. The electric car has become a great trend to replace the oil car, and with the increasing maturity of lithium battery technology, the electric car heat has further been pushed to the climax. The demand of batteries is increased rapidly, and especially the demand of lithium batteries is more insufficient, and the matched electrolyte is also in the rise of water. The research of battery electrolytes should not be merely a product that is dominant in the market economy, but should not be merely on a demand basis. The battery has excellent performance, not only is the design and the electrode dominant, but also the performance of the electrolyte is of decisive significance, so that the research of the electrolyte is serious and long.
Nowadays, lithium batteries take the leading role in the battery industry, the preparation methods of various electrolytes are endless, and the synthesis of lithium hexafluorophosphate, lithium difluorosulfimide and the like is more popular; lithium bis (fluorosulfonyl imide) is used as an electrolyte additive, and is accepted by the market due to the excellent product performance, the market demand is increased,
in the existing synthesis of lithium bis (fluorosulfonyl) imide, two common routes are a thionyl chloride method and an isocyanate method:
isocyanate process: although side reactions are few, impurities are few, post-treatment is relatively simple, raw materials are expensive, and it is difficult to maintain competitiveness in the market.
Sulfoxide chloride process: the raw materials are low in price, the reaction difficulty is relatively small, the raw materials are accepted by more and more people, and the raw materials are a mainstream production route of the industry. In the synthesis route of the thionyl chloride method, the dichlorsulfimide is an extremely important intermediate product, and the product index directly influences the operation of the subsequent reaction steps and the quality of the final product. However, in the chlorination reaction process, because the reaction time is longer, the temperature is relatively higher, the side reaction is more, and more multi-component impurities can be generated, so that the impurities not only affect the subsequent reaction and the product quality, but also have great potential safety hazards to industrial production.
Patent CN115304039a provides a method for purifying dichlorsulfoximine, which adopts a melting crystallizer, a falling film evaporator and other devices to operate, and removes heavy component impurities of dichlorsulfoximine, and the method can purify the purity to 99.5%, but has complex operation flow, and more impurities still exist in the final product.
Accordingly, in the art, for this mainstream route, it is desirable to develop an economical and efficient method for reducing the heavy component impurity content in the bischlorosulfonimide product.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for removing impurities of dichloro sulfimide. The invention takes the tantalum and niobium modified mesoporous molecular sieve as the adsorbent, and can rapidly adsorb tar heavy component impurities such as dichloro dimer, dichloro trimer and the like in the coarse dichloro sulfimide prepared by the thionyl chloride method.
The invention provides a method for removing impurities from dichlorosulfimide, which uses a mesoporous molecular sieve modified by tantalum and/or niobium as an adsorbent to adsorb impurities in a crude product of the dichlorosulfimide prepared by a thionyl chloride method.
In the impurity removal method, the mass percentage composition of the coarse product of the dichlorsulfonyl imide prepared by the thionyl chloride method comprises 10-99.5%, preferably 95-99.5% of dichlorsulfonyl imide; 0-60wt%, preferably 0-40wt% of thionyl chloride; 0-5wt%, preferably 0-2wt%, chlorosulfonic acid, 0-5wt%, preferably 0-3wt% sulfamic acid; 0.5-10%, preferably 0.5-5% of impurities; wherein the impurities comprise heavy tar components such as dichloro dimer, dichloro trimer and the like.
The process is the prior art, and the specific preparation process is not limited. The crude product of the dichlorsulfimide can be reaction liquid obtained by directly reacting thionyl chloride, chlorosulfonic acid and sulfamic acid, and can also be a secondary pure product obtained by rectifying and removing unreacted raw materials such as thionyl chloride, chlorosulfonic acid and sulfamic acid, and the like, so long as the materials in the concentration range prepared by the thionyl chloride method reaction belong to the crude product suitable for the impurity removal method, the crude product can be liquid or solid, and when the crude product is solid, the crude product can be melted into liquid at the adsorption temperature and is subjected to adsorption impurity removal treatment.
In the impurity removal method, the metal tantalum and/or niobium modified mesoporous molecular sieve has the content of 0.5-20wt%, preferably 5-16wt%;
preferably, the mesoporous molecular sieve has a pore size of 2-11nm, more preferably SBA-15 and/or MCM-41;
more preferably, the metallic tantalum and/or niobium modified mesoporous molecular sieve is selected from tantalum modified SBA-15 and/or niobium modified MCM-41;
the metallic tantalum and/or niobium modified mesoporous molecular sieve can be prepared by adopting a conventional method disclosed in the prior art, such as an impregnation method, and the invention is not particularly limited. In some specific examples of the invention, the metallic tantalum and/or niobium modified mesoporous molecular sieve may be prepared by the following method, including the steps of:
1) Adding the mesoporous molecular sieve into sodium hydroxide aqueous solution for soaking and eluting, then washing with water to be neutral, and drying to constant weight;
2) Placing the mesoporous molecular sieve treated in the step 1) into an aqueous solution of soluble salts of metal tantalum and/or niobium, fully stirring, and then adopting ammonia water to adjust the pH value to 9-11;
3) And 2) carrying out spin drying, filtering and drying on the system, calcining in an air environment, and then transferring into hydrogen-nitrogen mixed gas for roasting to obtain the metal tantalum and/or niobium modified mesoporous molecular sieve.
Preferably, in step 1), the aqueous sodium hydroxide solution has a concentration of 0.5 to 2mol/L, preferably 1 to 1.5mol/L.
Preferably, in step 1), the immersion elution time is from 1 to 12 hours, preferably from 4 to 8 hours.
Preferably, in step 2), the aqueous solution of soluble salts of metallic tantalum and/or niobium, wherein the total concentration of soluble salts of tantalum and soluble salts of niobium is between 1 and 20wt%, preferably between 5 and 16wt%;
more preferably, the soluble salts are hydrochlorides, fluorinated salts, such as tantalum pentafluoride, niobium chloride.
Preferably, in step 2), the stirring is carried out at a temperature of 40-70 ℃, preferably 45-60 ℃, for a time of 10-60min, preferably 30-50min.
Preferably, in step 2), the ammonia concentration is between 10 and 25wt%, preferably between 15 and 20wt%; the pH is adjusted at a system temperature of 40-70 ℃, preferably 50-60 ℃.
Preferably, in step 3), the calcination is carried out at a temperature of 400-700 ℃, preferably 500-600 ℃, for a time of 1-12 hours, preferably 6-10 hours.
Preferably, in step 3), the calcination is carried out at a temperature of 400-600 ℃, preferably 400-500 ℃, for a time of 1-10 hours, preferably 4-8 hours;
the hydrogen-nitrogen mixture gas contains hydrogen in an amount of 0.5 to 5wt%, preferably 2 to 4wt%.
The preparation method of the metal tantalum and/or niobium modified mesoporous molecular sieve also comprises the conventional operations in the field such as water washing, drying, spin drying, filtering and the like, and the preparation method is not particularly required.
The mesoporous molecular sieve modified by the metal tantalum and/or the niobium is pretreated and eluted by a sodium hydroxide aqueous solution with proper concentration during preparation, and then a proper amount of the metal tantalum and/or the niobium is introduced to fill the mesoporous molecular sieve, so that the mesoporous molecular sieve can completely replace the original aluminum atoms, construct a new metal frame and etch a new pore canal; the metal framework newly constructed by the method has a more stable structure, and then a new pore canal is formed by a proper replacement mode, a dispersion mode, etching and calcining temperature, so that the prepared modified mesoporous molecular sieve has better adsorption effect on heavy component tar macromolecular impurities such as dichloro dimer, dichloro trimer and the like in the system; meanwhile, the modified metal tantalum and/or niobium introduced by the invention can be subjected to complexation adsorption with heavy components in raw materials to improve adsorption efficiency, and can also form a more stable new bond with silicon oxygen atoms in the molecular sieve, so that the adsorbent can maintain long service life under the strong corrosion system.
In the impurity removal method of the invention, the adsorption temperature is 30-100 ℃, preferably 40-70 ℃, and the pressure is 0.1-5MPaG, preferably 0.3-3MPaG; the adsorption residence time is 70-720s, preferably 180-360s;
the mass airspeed of the adsorption process is 5-50h -1 Preferably 10-20h -1 。
Preferably, the adsorption is performed in a nitrogen atmosphere.
The adsorption process is carried out in an adsorption device, the type of the adsorption device has little influence on the impurity removal effect, and the adsorption process can be a fixed bed, a reaction kettle and the like, and the invention is not particularly limited;
in the adsorption process, the required adsorption raw materials enter a heating premixing zone, after the premixing zone is premixed to a specified temperature, the raw materials before adsorption pass through an adsorbent filling zone according to a preset flow through a feed pump, the adsorbent filling zone maintains the adsorption temperature through heat tracing, the adsorption pressure is maintained through inert gas, and standard products in a discharge zone are extracted through a discharge pump.
The content of tar impurities of heavy components such as dichloro dimer, dichloro trimer and the like in the product obtained by the impurity removal method can be reduced to below 0.05 percent by taking the mass of unreacted raw materials such as thionyl chloride, chlorosulfonic acid, sulfamic acid and the like as a reference.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the method can quickly remove heavy component impurities such as tar in the crude raw material without introducing new impurities, so that the impurities are removed in advance, the impurities are not required to be brought into subsequent application, the impurity removal effect is obvious, the production cost is low, and the adsorbent can well resist a strong corrosion system of the raw material.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The main raw material source information adopted in the embodiment of the invention is as follows, and other raw materials are common commercial raw materials unless specified otherwise:
mesoporous molecular sieve SBA-15, pore diameter is 3.5-10nm, brand: INNOCHEM, cat: SBA-15;
mesoporous molecular sieve MCM-41 molecular sieve with aperture of 2-8nm, brand: gram-number: 105120;
tantalum fluoride, brand: ALFA, cat No.: 014052, purity: 99.9%;
niobium pentachloride, brand: innochem, cat No.: a81205, purity: 99.9%;
the preparation process of the coarse product of the thionyl chloride process dichlorinated sulfimide comprises the following steps: the catalyst is prepared by reacting thionyl chloride, sulfamic acid and chlorosulfonic acid at a proper temperature according to a certain proportion; the crude product is as follows: removing the solvent from the residue after rectification and purification, or adding heavy component into the residue after long-time distillation.
The experimental procedures referred to in the following examples or comparative examples are conventional experimental methods in the art unless otherwise specified.
The analysis method comprises the following steps: nuclear magnetic instrument: bruker AVANCE III 400M configuration: ULTRASHIELD 400 magnet/B-ACS 60 bit autosampler/Topstin 3.0 software/5 mm Dual (13C, 1H) Dual core probe/5 mm BBO probe.
Example 1
Tantalum modified SBA-15 molecular sieve (adsorbent 1) with the steps of:
1) Adding SBA-15 molecular sieve into 1.2mol/L sodium hydroxide aqueous solution for soaking and eluting for 7h, then leaching with ultrapure water to neutrality, and baking at 120 ℃ to constant weight;
2) Placing the SBA-15 molecular sieve treated in the step 1) into a tantalum fluoride aqueous solution with the concentration of 16wt%, fully stirring for 45min at 50 ℃, then dropwise adding ammonia water with the concentration of 18wt% under the condition to adjust the pH to 9-11, performing spin-drying filtration, drying to constant weight at 120 ℃, calcining for 9h at 550 ℃, then introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 3.5wt%, and continuously roasting for 8h at 490 ℃ to obtain the tantalum modified SBA-15, wherein the tantalum content is 11wt%.
Example 2
The preparation method of the niobium modified MCM-41 molecular sieve (adsorbent 2) comprises the following steps:
1) Adding the MCM-41 molecular sieve into a sodium hydroxide aqueous solution with the concentration of 2mol/L for soaking and eluting for 1h, then leaching with ultrapure water to be neutral, and baking at 100 ℃ to constant weight;
2) Placing the MCM-41 molecular sieve treated in the step 1) into a niobium chloride aqueous solution with the concentration of 5wt%, fully stirring for 60min at 40 ℃, then dropwise adding ammonia water with the concentration of 10wt% under the condition to adjust the pH to 9-11, performing spin drying filtration, drying to constant weight at 100 ℃, calcining for 1h at 700 ℃, then introducing a hydrogen-nitrogen mixture with the hydrogen content of 0.5wt%, and continuously roasting for 4h at 400 ℃ to obtain the niobium modified ZSM-5, wherein the niobium content is 4.0wt%.
Example 3
The preparation method of the tantalum modified MCM-41 molecular sieve (adsorbent 3) comprises the following steps:
1) Adding the MCM-41 molecular sieve into a sodium hydroxide aqueous solution with the concentration of 0.5mol/L for soaking and eluting for 12 hours, then leaching with ultrapure water to be neutral, and baking at 130 ℃ to constant weight;
2) Placing the MCM-41 molecular sieve treated in the step 1) into a tantalum pentachloride aqueous solution with the concentration of 20wt%, fully stirring for 60min at 40 ℃, then dropwise adding ammonia water with the concentration of 25wt% to adjust the pH to 9-11 under the condition, performing spin drying filtration, drying to constant weight at 100 ℃, calcining for 10h at 400 ℃, then introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 0.5wt%, and continuously roasting for 10h at 500 ℃ to obtain the niobium modified MCM-41, wherein the tantalum content is 12.5wt%.
Example 4
The preparation of the niobium modified SBA-15 molecular sieve (adsorbent 4) comprises the following steps:
1) Adding SBA-15 molecular sieve into 1.5mol/L sodium hydroxide aqueous solution for soaking and eluting for 6 hours, then leaching with ultrapure water to neutrality, and baking at 100 ℃ to constant weight;
2) Placing the SBA-15 molecular sieve treated in the step 1) into a niobium chloride aqueous solution with the concentration of 3wt%, fully stirring for 60min at 40 ℃, then dropwise adding ammonia water with the concentration of 20wt% to adjust the pH to 9-11 under the condition, performing spin drying filtration, drying to constant weight at 100 ℃, calcining for 1h at 700 ℃, then introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 0.5wt%, and continuously roasting for 4h at 550 ℃ to obtain the niobium modified SBA-15, wherein the niobium content is 2.5wt%.
Example 5
The crude product (refined product after rectification) of the dichlorsulfoimide comprises the following components in percentage by mass: 97.5wt% of dichlorinated sulfimide and 2.5wt% of impurities (including dichlorinated dimer and dichlorinated trimer).
The method comprises the following steps of:
the crude product is preheated to 50 ℃ and then pumped into an adsorption device by a feed pump, and simultaneously nitrogen is introduced to control the pressure of 2MPaG, the temperature of 60 ℃, and the crude product is respectively adsorbed and purified by the adsorption areas of the adsorbents 1-4 prepared in the examples 1-4, and the space velocity is 15h -1 The adsorption residence time was 240S, and after the device was stably operated, the impurity content in the product was sampled and detected in the product discharge zone, and the results are shown in table 1.
The adsorption performance decay rate and the dissolution loss rate were measured after continuous operation for 100 hours, and the results are shown in Table 1.
TABLE 1
| Adsorbent and process for producing the same | Impurity content/% | Adsorption performance decay rate/% | Dissolution loss rate/% |
| Adsorbent 1 | 0.01 | 1 | 0.1 |
| Adsorbent 2 | 0.04 | 2 | 0.15 |
| Adsorbent 3 | 0.03 | 1.5 | 0.15 |
| Adsorbent 4 | 0.05 | 1.8 | 0.1 |
Example 6
The mass percentage of the crude product (reaction liquid) of the dichlorsulfimide comprises: 89wt% of dichlorsulfimide and 8.5wt% of thionyl chloride; 0.5wt% of chlorosulfonic acid and 0.5wt% of sulfamic acid; 1.5wt% of impurities (including dichloro dimers, dichloro trimers);
the crude product is preheated to 50 ℃ and then pumped into an adsorption device by a feed pump, and simultaneously nitrogen is introduced to control the pressure of 2MPaG, the temperature of 60 ℃, and the crude product is respectively adsorbed and purified by the adsorption areas of the adsorbents 1-4 prepared in the examples 1-4, and the space velocity is 15h -1 The adsorption residence time was 240S, and after the apparatus was stably operated, the impurity content in the product (calculated based on the mass of the product after deducting unreacted raw materials such as thionyl chloride, chlorosulfonic acid, sulfamic acid, etc.) was sampled and detected in the product discharge zone, and the results are shown in table 2.
The adsorption performance decay rate and the dissolution loss rate were measured after continuous operation for 100 hours, and the results are shown in Table 2.
TABLE 2
| Adsorbent and process for producing the same | Impurity content/% | Adsorption performance decay rate/% | Dissolution loss rate/% |
| Adsorbent 1 | 0.01 | 1 | 0.1 |
| Adsorbent 2 | 0.02 | 1.5 | 0.1 |
| Adsorbent 3 | 0.01 | 1 | 0.1 |
| Adsorbent 4 | 0.04 | 1.3 | 0.1 |
Example 7
The crude product (refined product after rectification) of the dichlorsulfoimide comprises the following components in percentage by mass: 99.5wt% of dichlorinated sulfimide and 0.5wt% of impurities (comprising dichlorinated dimer and dichlorinated trimer).
The method comprises the following steps of:
the crude product is preheated to 30 ℃ and then pumped into an adsorption device by a feed pump, and simultaneously nitrogen is introduced to control the pressure to 0.1MPaG, the temperature is 30 ℃, and the crude product is adsorbed and purified by the adsorption areas of the adsorbents 1 to 4 prepared in the examples 1 to 4 respectively, and the airspeed is 50h -1 The adsorption residence time was 72S, and after the device was stably operated, the impurity content in the product was sampled and detected in the product discharge zone, and the results are shown in table 3.
The adsorption performance decay rate and the dissolution loss rate were measured after continuous operation for 100 hours, and the results are shown in Table 3.
TABLE 3 Table 3
| Adsorbent and process for producing the same | Impurity content/% | Adsorption performance decay rate/% | Dissolution loss rate/% |
| Adsorbent 1 | 0.01 | 1.5 | 0.15 |
| Adsorbent 2 | 0.02 | 1.9 | 0.18 |
| Adsorbent 3 | 0.01 | 1.5 | 0.13 |
| Adsorbent 4 | 0.03 | 1.8 | 0.12 |
Example 8
The mass percentage of the crude product (reaction liquid) of the dichlorsulfimide comprises: 15wt% of dichlorsulfimide and 83wt% of thionyl chloride; 0.7wt% of chlorosulfonic acid and 0.8wt% of sulfamic acid; 0.5wt% of impurities (including dichloro dimers, dichloro trimers);
the crude product was preheated to 30deg.C and pumped into an adsorption apparatus with a feed pump while introducing nitrogen at a controlled pressure of 5MPaG at 30deg.C, and the impurities were removed by adsorption through the adsorption zones of adsorbents 1 to 4 prepared in examples 1 to 4, respectively, at a space velocity of 15h -1 The adsorption residence time was 240S, and after the apparatus was stably operated, the impurity content in the product was sampled and detected in the product discharge zone based on the mass of the product after deducting unreacted raw materials such as thionyl chloride, chlorosulfonic acid, sulfamic acid, etc.), and the results were shown in table 4.
The adsorption performance decay rate and the dissolution loss rate were measured after continuous operation for 100 hours, and the results are shown in Table 4.
TABLE 4 Table 4
| Adsorbent and process for producing the same | Impurity content/% | Adsorption performance decay rate/% | Dissolution loss rate/% |
| Adsorbent 1 | 0.02 | 1 | 0.05 |
| Adsorbent 2 | 0.03 | 1.5 | 0.05 |
| Adsorbent 3 | 0.02 | 1.9 | 0.1 |
| Adsorbent 4 | 0.03 | 1.1 | 0.05 |
Example 9
The crude product (refined product after rectification) of the dichlorsulfoimide comprises the following components in percentage by mass: 95.5wt% of dichlorsulfoimide and 4.5wt% of impurities (including dichlorinated dimer and dichlorinated trimer).
The method comprises the following steps of:
the crude product is preheated to 60 ℃ and then pumped into an adsorption device by a feed pump, and simultaneously nitrogen is introduced to control the pressure to be 3Mpa and the temperature to be 70 ℃, and the adsorption zone of the adsorbents 1 to 4 prepared in examples 1 to 4 is used for adsorption impurity removal, and the space velocity is 5h -1 The adsorption residence time was 720S, and after the device was stably operated, the impurity content in the product was sampled and detected in the product discharge zone, and the results are shown in table 5.
The adsorption performance decay rate and the dissolution loss rate were measured after continuous operation for 100 hours, and the results are shown in Table 5.
TABLE 5
| Adsorbent and process for producing the same | Impurity content/% | Adsorption performance decay rate/% | Dissolution loss rate/% |
| Adsorbent 1 | 0.01 | 1.1 | 0.1 |
| Adsorbent 2 | 0.02 | 1.2 | 0.15 |
| Adsorbent 3 | 0.01 | 1.5 | 0.15 |
| Adsorbent 4 | 0.03 | 1.8 | 0.1 |
Example 10
The mass percentage of the crude product (reaction liquid) of the dichlorsulfimide comprises: 35wt% of dichlorsulfimide and 59wt% of thionyl chloride; 1.1wt% of chlorosulfonic acid and 1.4wt% of sulfamic acid; 3.5wt% of impurities (including dichloro dimers, dichloro trimers);
the crude product is preheated to 60 ℃ and then pumped into an adsorption device by a feed pump, and simultaneously nitrogen is introduced to control the pressure to 5MPaG, the temperature to 70 ℃, and the crude product is respectively adsorbed and purified by the adsorption areas of the adsorbents 1 to 4 prepared in the examples 1 to 4, and the airspeed is 15h -1 The adsorption residence time was 240S, and after the apparatus was stably operated, the impurity content in the product was sampled and detected in the product discharge zone based on the mass of the product after deducting unreacted raw materials such as thionyl chloride, chlorosulfonic acid, sulfamic acid, etc.), and the results were shown in table 6.
The adsorption performance decay rate and the dissolution loss rate were measured after continuous operation for 100 hours, and the results are shown in Table 6.
TABLE 6
| Adsorbent and process for producing the same | Impurity content/% | Adsorption performance decay rate/% | Dissolution loss rate/% |
| Adsorbent 1 | 0.01 | 1.2 | 0.1 |
| Adsorbent 2 | 0.04 | 1.1 | 0.15 |
| Adsorbent 3 | 0.03 | 1.3 | 0.1 |
| Adsorbent 4 | 0.05 | 1.2 | 0.1 |
Comparative example 1
The adsorbent was prepared by the method of reference example 1, except that: and replacing the SBA-15 mesoporous molecular sieve with a 5A molecular sieve, and preparing the tantalum modified 5A molecular sieve without changing other operations.
Impurity removal is carried out on the secondary purity of the dichlorsulfoimide by referring to the method of the example 5, the adsorbent is replaced by the prepared tantalum modified 5A molecular sieve adsorbent, other operations and conditions are unchanged, and the impurity content in the treated product is 2.1wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 60.5%, and the dissolution loss rate is 2.5%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, and replacing the adsorbent with the prepared tantalum-modified 5A molecular sieve adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.5wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 30.6%, and the dissolution loss rate is 2.2%.
Comparative example 2
The adsorbent was prepared by the method of reference example 1, except that: and replacing the SBA-15 mesoporous molecular sieve with a 4A molecular sieve, and preparing the tantalum modified 4A molecular sieve without changing other operations.
Impurity removal is carried out on the secondary purity of the dichlorsulfoximine by referring to the method of the example 5, the adsorbent is replaced by the prepared tantalum modified 4A molecular sieve adsorbent, other operations and conditions are unchanged, and the impurity content in the treated product is 2.45wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 27.6%, and the dissolution loss rate is 1.9%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, and replacing the adsorbent with the prepared tantalum-modified 4A molecular sieve adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.56wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 28.4%, and the dissolution loss rate is 2.2%.
Comparative example 3
The adsorbent was prepared by the method of reference example 1, except that: the SBA-15 mesoporous molecular sieve is replaced by a microporous molecular sieve ZSM-5 with the aperture of about 0.55nm, and other operations are unchanged, so that the tantalum modified ZSM-5 molecular sieve is prepared.
Impurity removal is carried out on the sub-pure dichlorsulfoimide product by the method of the example 5, the adsorbent is replaced by the prepared tantalum modified adsorbent, other operation and conditions are unchanged, and the impurity content in the treated product is 2.3wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 15%, and the dissolution loss rate is 1.0%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, and replacing the adsorbent with the prepared tantalum-modified ZSM-5 adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.61wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 21.2%, and the dissolution loss rate is 2.1%.
Comparative example 4
The adsorbent was prepared by the method of reference example 1, except that: the modified metal tantalum is replaced by vanadium, and other operations are unchanged, so that the vanadium modified SBA-15 molecular sieve is prepared.
Impurity removal is carried out on the secondary purity of the dichlorsulfoximine by referring to the method of the example 5, the adsorbent is replaced by the prepared vanadium-modified SBA-15 molecular sieve adsorbent, other operation and conditions are unchanged, and the impurity content in the treated product is 2.2wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 36%, and the dissolution loss rate is 0.5%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, and replacing the adsorbent with the prepared vanadium-modified SBA-15 molecular sieve adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.9wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 33.4%, and the dissolution loss rate is 0.4%.
Comparative example 5
The adsorbent was prepared by the method of reference example 1, except that: and replacing the modified metal tantalum with molybdenum, and preparing the molybdenum modified SBA-15 molecular sieve without changing other operations.
Impurity removal is carried out on the sub-pure dichlorsulfoimide product by referring to the method of the example 5, the adsorbent is replaced by the prepared molybdenum modified SBA-15 molecular sieve adsorbent, other operation and conditions are unchanged, and the impurity content in the treated product is 2.4wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 20.6%, and the dissolution loss rate is 0.4%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, and replacing the adsorbent with the prepared molybdenum-modified SBA-15 molecular sieve adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.46wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 29.2.1 percent and the dissolution loss rate is 0.6 percent.
Comparative example 6
Example 5 the procedure was used to remove impurities from a sub-purity bis-chlorosulfonyl imide product with the only difference that: directly adopting unmodified SBA-15 as an adsorbent, keeping other operation and conditions unchanged, wherein the impurity content in the treated product is 2.4wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 19.6%, and the dissolution loss rate is 0.1%.
The reaction solution of bischlorosulfonimide was purified by the method of example 6, except that: directly adopting unmodified SBA-15 as an adsorbent, keeping other operation and conditions unchanged, wherein the impurity content in the treated product is 1.57wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 20.7%, and the dissolution loss rate is 0.1%.
Comparative example 7
Example 5 the procedure was used to remove impurities from a sub-purity bis-chlorosulfonyl imide product with the only difference that: directly adopting unmodified MCM-41 as an adsorbent, keeping other operation and conditions unchanged, wherein the impurity content in the treated secondary pure product is 2.3wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 24.5%, and the dissolution loss rate is 0.1%.
The reaction solution of bischlorosulfonimide was purified by the method of example 6, except that: directly adopting unmodified MCM-41 as an adsorbent, keeping other operation and conditions unchanged, wherein the impurity content in the treated product is 1.41wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 23.7%, and the dissolution loss rate is 0.1%.
Comparative example 8
The adsorbent was prepared by the method of reference example 1, except that: the preparation process does not adopt the step 1) alkali soaking and elution, and other operations are unchanged, so that the tantalum modified SBA-15 molecular sieve is prepared.
Impurity removal is carried out on the sub-pure dichlorsulfoimide product by referring to the method of the example 5, the adsorbent is replaced by the prepared tantalum modified SBA-15 molecular sieve adsorbent, other operation and conditions are unchanged, and the impurity content in the treated product is 2.35wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 32.7%, and the dissolution loss rate is 1.5%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, replacing the adsorbent with the prepared tantalum modified SBA-15 molecular sieve adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.55wt%; after continuous operation for 100 hours, the adsorption performance attenuation rate is 29.3 percent, and the dissolution loss rate is 1.7 percent.
Comparative example 9
The adsorbent was prepared by the method of reference example 1, except that: the preparation process step 2) has no roasting operation, and other operations are unchanged, so that the tantalum modified SBA-15 molecular sieve is prepared.
Impurity removal is carried out on the sub-pure dichlorsulfoimide product by referring to the method of the example 5, the adsorbent is replaced by the prepared tantalum modified SBA-15 molecular sieve adsorbent, other operation and conditions are unchanged, and the impurity content in the treated product is 1.2wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 5.4%, and the dissolution loss rate is 1.7%.
Removing impurities from the dichloro-sulphonyl-imide reaction solution by referring to the method of the example 6, replacing the adsorbent with the prepared tantalum modified SBA-15 molecular sieve adsorbent, wherein other operations and conditions are unchanged, and the impurity content in the treated product is 1.1wt%; and after the continuous operation is carried out for 100 hours, the adsorption performance attenuation rate is 7.6%, and the dissolution loss rate is 1.3%.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (10)
1. The impurity removing method for the dichlorosulfimide is characterized in that a mesoporous molecular sieve modified by tantalum and/or niobium is used as an adsorbent to adsorb impurities in a crude product of the dichlorosulfimide prepared by a thionyl chloride method.
2. The method for removing impurities according to claim 1, wherein the crude product of the dichlorsulfonylimide prepared by the thionyl chloride method comprises, by mass, 10-99.5%, preferably 95-99.5% of dichlorsulfonylimide; 0-60wt%, preferably 0-40wt% of thionyl chloride; 0-5wt%, preferably 0-2wt%, chlorosulfonic acid, 0-5wt%, preferably 0-3wt% sulfamic acid; the impurity is 0.5-10%, preferably 0.5-5%.
3. The process for removing impurities according to claim 1 or 2, characterized in that the metallic tantalum and/or niobium modified mesoporous molecular sieve has a content of metallic tantalum and/or niobium of 0.5-20wt%, preferably 5-16wt%;
preferably, the mesoporous molecular sieve has a pore size of 2-11nm, more preferably SBA-15 and/or MCM-41.
4. A process according to any one of claims 1 to 3, wherein the metallic tantalum and/or niobium modified mesoporous molecular sieve is selected from tantalum modified SBA-15 and/or niobium modified MCM-41.
5. The method of any one of claims 1-4, wherein the metallic tantalum and/or niobium modified mesoporous molecular sieve is prepared by a method comprising the steps of:
1) Adding the mesoporous molecular sieve into sodium hydroxide aqueous solution for soaking and eluting, then washing with water to be neutral, and drying to constant weight;
2) Placing the mesoporous molecular sieve treated in the step 1) into an aqueous solution of soluble salts of metal tantalum and/or niobium, fully stirring, and then adopting ammonia water to adjust the pH value to 9-11;
3) And 2) carrying out spin drying, filtering and drying on the system, calcining in an air environment, and then transferring into hydrogen-nitrogen mixed gas for roasting to obtain the metal tantalum and/or niobium modified mesoporous molecular sieve.
6. The method according to any one of claims 1 to 5, wherein in step 1), the aqueous sodium hydroxide solution has a concentration of 0.5 to 2mol/L, preferably 1 to 1.5mol/L;
in step 1), the immersion elution time is 1 to 12 hours, preferably 4 to 8 hours.
7. The process of any one of claims 1 to 6, wherein in step 2) the aqueous solution of soluble salts of metallic tantalum and/or niobium, wherein the total concentration of soluble salts of tantalum and soluble salts of niobium is 1-20wt%, preferably 5-16wt%;
preferably, the soluble salts are hydrochlorides, fluorinated salts, such as tantalum pentafluoride, niobium chloride;
in step 2), the temperature is 40-70 ℃, preferably 45-60 ℃ and the time is 10-60min, preferably 30-50min;
in step 2), the concentration of the aqueous ammonia is 10 to 25wt%, preferably 15 to 20wt%; the pH is adjusted at a system temperature of 40-70 ℃, preferably 50-60 ℃.
8. The process according to any one of claims 1 to 7, wherein in step 3) the calcination is carried out at a temperature of 400 to 700 ℃, preferably 500 to 600 ℃, for a time of 1 to 12 hours, preferably 6 to 10 hours;
in step 3), the calcination is carried out at a temperature of 400-600 ℃, preferably 400-500 ℃ for a time of 1-10 hours, preferably 4-8 hours;
the hydrogen-nitrogen mixture gas contains hydrogen in an amount of 0.5 to 5wt%, preferably 2 to 4wt%.
9. The process according to any one of claims 1 to 8, wherein the adsorption is carried out at a temperature of 30-100 ℃, preferably 40-70 ℃, and a pressure of 0.1-5mpa g, preferably 0.3-3mpa g; the adsorption residence time is 70-720s, preferably 180-360s;
preferably, the adsorption is performed in a nitrogen atmosphere.
10. The process of any one of claims 1 to 9, wherein the adsorption process has a mass space velocity of 5 to 50 hours -1 Preferably 10-20h -1 。
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