CN115920977B - Forming method of spherical alumina carrier - Google Patents
Forming method of spherical alumina carrier Download PDFInfo
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- CN115920977B CN115920977B CN202110945743.6A CN202110945743A CN115920977B CN 115920977 B CN115920977 B CN 115920977B CN 202110945743 A CN202110945743 A CN 202110945743A CN 115920977 B CN115920977 B CN 115920977B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 80
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000008188 pellet Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000001935 peptisation Methods 0.000 claims abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 127
- 238000000465 moulding Methods 0.000 claims description 89
- 239000003921 oil Substances 0.000 claims description 52
- 229910021529 ammonia Inorganic materials 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 31
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 239000000843 powder Substances 0.000 description 25
- 239000012046 mixed solvent Substances 0.000 description 20
- 239000007863 gel particle Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 238000004537 pulping Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000003672 processing method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229960004011 methenamine Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- WCGUUGGRBIKTOS-GPOJBZKASA-N (3beta)-3-hydroxyurs-12-en-28-oic acid Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C WCGUUGGRBIKTOS-GPOJBZKASA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229940096998 ursolic acid Drugs 0.000 description 1
- PLSAJKYPRJGMHO-UHFFFAOYSA-N ursolic acid Natural products CC1CCC2(CCC3(C)C(C=CC4C5(C)CCC(O)C(C)(C)C5CCC34C)C2C1C)C(=O)O PLSAJKYPRJGMHO-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
The invention relates to a forming method of spherical alumina, which comprises the following steps: (1) Mixing hydrated alumina with deionized water to obtain a suspension, stirring, and adding an acid solution to carry out peptization to obtain alumina sol; (2) And (3) dripping the alumina sol prepared in the step (1) into a forming device for forming, wherein the forming liquid is a quasi-homogeneous organic solution formed by fully mixing ammonia gas and an oil phase, taking out formed pellets, and drying and roasting to obtain the spherical alumina carrier. The forming method of the spherical alumina provided by the invention has the advantages of environmental protection, high production efficiency and high sphericity of products.
Description
Technical Field
The invention relates to a preparation method of a spherical carrier, in particular to a forming method of a high-purity spherical alumina carrier.
Background
Spherical alumina is widely used as an adsorbent, a catalyst, a carrier, etc. because of its high specific surface area and excellent pore structure characteristics. The spherical shape can effectively reduce the abrasion among particles and reduce the generation of dust, and the advantages are more obvious when the spherical shape is particularly used for a moving bed. At present, the common forming methods of alumina pellets mainly comprise an oil ammonia column method and a hot oil column method.
The general flow of the oil ammonia column forming is as follows: and (3) dripping the aluminum sol into an oil ammonia column to enable the sol to be formed into balls in an oil phase at the upper layer of the oil ammonia column and to be gelled in ammonia water at the lower layer. And (3) drying and roasting the gelled particles after ageing to obtain spherical gamma-Al 2O3. US4542113 discloses a preparation method of spherical alumina, which comprises the steps of dripping alumina sol containing 20-40 wt% of alumina and 1-10 wt% of urea into an upper oil phase and a lower ammonia water forming column, wherein the oil phase accounts for 10-50%, preferably diesel oil, gas oil, coal oil and the like, the ammonia water accounts for 50-90%, the concentration is 1-10 wt%, preferably 8wt%, and 0.1% of surfactant Alfol 610-4.5EO is added into the ammonia water. The alumina pellets prepared by the method have high strength and excellent pore structure.
In order to enable sol particles to smoothly pass through an oil-water interface, a surfactant is often added at the interface to reduce the interfacial tension, but the introduction of the surfactant is easy to cause oil-water emulsification, so that oil phase turbidity is deteriorated, the balling rate is reduced, and impurities can be possibly brought to the sol particles. CN1493524a discloses a method for forming spherical alumina by using an oil ammonia column, which comprises the steps of dripping aluminum sol into an oil ammonia column composed of an upper layer oil phase with the thickness of 0.1-4.5 mm and a lower layer electrolyte solution with the thickness of 10-300 cm, aging, drying and roasting to obtain the product. The oil phase of the method does not contain surfactant, the purity of the obtained product is higher, but the oil layer is too thin to realize circulation, and industrialization is difficult to realize.
CN103011213 describes an oil ammonia column forming method using a nonionic surfactant, wherein an aluminum sol and the nonionic surfactant are simultaneously dripped into the oil ammonia column, wherein the nonionic surfactant is dissolved in a mixed solvent of alcohol and water, and the nonionic surfactant can be alkylphenol ethoxylate or fatty alcohol ethoxylate. The method has higher balling rate, no impurity ions are introduced, no water washing is needed after molding, more organic matters are needed to be added in the process, and the method is complex in operation and higher in cost.
The oil ammonia column method has the advantages of uniform structure, low abrasion and high strength, but a large amount of ammonia water is needed in the forming process, the ammonia water is easy to volatilize in the circulating process to cause environmental pollution, and the existence of interfacial tension between oil and water brings great difficulty to the serialization and industrialization of the oil ammonia column forming.
The process of hot oil column forming is generally as follows: the aluminum sol and the gelatinizer (hexamethylenetetramine, also called as ursolic acid) are fully stirred to obtain an aluminum sol mixture with proper viscosity and solid content, the mixture is dripped into a hot oil column device with the temperature of 90-95 ℃ to shrink into balls, and the balls are aged, washed, dried and roasted to obtain the gamma-Al 2O3 balls. US2620314 discloses a hot oil column forming method for preparing alumina pellets, which comprises mixing hexamethylenetetramine as a gelling agent in an aluminum sol, dripping the mixed aluminum sol into a hot oil column for forming, wherein the hexamethylenetetramine is gradually hydrolyzed at high temperature to release ammonia, so that sol particles have enough time for forming before gelation, and aging, alkaline washing, drying and roasting to obtain solid pellets. The method has the advantages of less equipment, simple and convenient operation and low labor intensity, but the gel agent is easy to decompose formaldehyde and ammonia gas in the forming process, thereby causing personal injury and environmental pollution; in addition, the oil product is liable to deteriorate during the long-time heating, resulting in a decrease in molding efficiency.
CN102718241a describes a method for forming spherical alumina by oil-water column, which uses the rapid sol-gel property of alginic acid to prepare spherical particles in water column. Adding pseudo-boehmite into an alginate solution to prepare alginic acid-pseudo-boehmite suspension, dripping the suspension into an aqueous solution of aluminum, calcium, barium, copper, zinc, manganese or cobalt metal ions with a certain concentration and pH value to form alginic acid-pseudo-boehmite composite pellets, and washing, drying and roasting the pellets to obtain spherical alumina. The method has high balling efficiency and no pollution, but the sphericity of gel particles is greatly different due to different binding modes of alginic acid and different metal cations, wherein the sphericity of the product is better when the product is molded in calcium and zinc ion solution, more impurity ions are introduced, and the impurity ions are not additionally introduced when the product is molded in aluminum ion solution, but the sphericity of the product is lower, and the purity and sphericity of the product cannot be both considered.
Disclosure of Invention
The invention aims to solve the problems of environmental pollution caused by volatilization of ammonia and emission of waste ammonia water in the process of forming an oil ammonia column and deterioration of forming oil caused by harmful gas decomposed by a gelatinizing agent in the process of forming the oil ammonia column, and provides a forming method of a spherical alumina carrier with environmental protection, high production efficiency and high sphericity of products.
For this purpose, the invention provides a method for forming spherical alumina, comprising the following steps:
(1) Mixing hydrated alumina with deionized water to obtain a suspension, stirring, and adding an acid solution to carry out peptization to obtain alumina sol;
(2) And (3) dripping the alumina sol prepared in the step (1) into a forming device for forming, wherein the forming liquid is a quasi-homogeneous organic solution formed by fully mixing ammonia gas and an oil phase, taking out the formed pellets, and aging, drying and roasting to obtain the spherical alumina carrier.
The molding method of the present invention, wherein preferably, the hydrated alumina is boehmite, pseudo-boehmite, or a mixture of both; high-purity alumina powder having a large specific surface area and a large pore volume, which is produced by an aluminum alkoxide hydrolysis method, is preferred.
The molding method of the present invention, wherein it is preferable that the solid content of the suspension in the step (1) is 20 to 40% by weight based on the mass of alumina.
The molding method of the present invention, wherein preferably, the solid content of the alumina sol is 10 to 30wt% in terms of alumina; further preferably, the aging is performed in an aqueous ammonia solution having a concentration of 6 to 10wt%, the aging is performed for 1 to 12 hours at a temperature of 20 to 40 ℃.
In the molding method of the present invention, it is preferable that the acid in the acid solution is nitric acid, hydrochloric acid, formic acid, acetic acid or perchloric acid, and further preferably nitric acid or hydrochloric acid, the mass concentration of the acid solution is 5 to 50wt%, and the amount of the acid solution is 0.04 to 0.1 when the molar ratio of H +/Al3+ in the alumina sol is satisfied.
In the molding method of the present invention, preferably, the oil phase in the quasi-homogeneous organic solution is at least one of heptane, octane, nonane, gasoline, kerosene, paraffin oil, mineral oil, and petroleum ether.
In the molding method of the present invention, preferably, in the step (2), the molding device includes a ball drop tray, a ball forming column and a dryer which are sequentially connected from top to bottom, the bottom of the ball forming column is communicated with the premixing device, and the upper ammonia gas and the lower organic phase are stored in the ball forming column, wherein the organic phase is the quasi-homogeneous organic solution.
Specifically, the forming device forms closed loop circulation, has good sealing, no liquid or gas leakage and good environmental protection effect.
The molding method of the invention is characterized in that the premixing device comprises an ammonia gas pipeline, an oil phase pipeline and a disperser, wherein the ammonia gas pipeline and the oil phase pipeline are connected in parallel to the disperser through a micro regulator, the disperser is connected with a balling column, and upper ammonia gas and lower organic phase in the balling column are respectively circulated into the disperser through a ball valve and a pump; further preferably, the disperser is made of ceramic, metal or film material; further preferably, the pump is a diaphragm pump, a slurry pump, a plunger pump or a water pump; further preferably, a drain outlet is arranged at the bottom of the dryer.
The molding method of the present invention, wherein preferably, the molding process comprises the steps of: introducing alumina sol into the ball-dropping disc of the forming device, then dripping the alumina sol into the ball-dropping column, shrinking the ball-dropping column to form balls under the action of oil phase in the ball-dropping column, and solidifying the balls under the action of ammonia dissolved in an organic solvent to form gel balls; and in the dripping process, the organic solvent is circulated into the disperser through a pump to be remixed with the ammonia gas, and the ammonia gas lost by the system is replenished through an ammonia gas pipeline.
In the molding method of the present invention, preferably, in the dropping process, the dropping speed is 1-2 kg/h based on the pseudo-boehmite mass, the circulation ratio of the pump is 0-0.20, and the ammonia flow rate of the ammonia gas pipeline is 20-50L/h.
Specifically, the dropping process is continuous operation, the alumina sol forms liquid drops through the dropping ball disc, the liquid drops enter a water-insoluble quasi-homogeneous organic solvent in a ball column through the action of gravity, shrink into balls under the action of surface tension, and meanwhile, the liquid drops are solidified into gel balls through neutralization reaction with NH 3 dissolved in the solvent. And the organic solvent is circulated into the disperser by a pump to be remixed with NH 3 in the process of dripping, the circulation ratio is 0-0.2 (reflux quantity/quantity of organic phase in the forming column), and the circulation quantity depends on the dripping speed, the acid aluminum ratio and the solubility of different solvents to NH 3. And opening an ammonia pipeline to supplement NH 3 lost by the system, wherein the flow rate of the ammonia is 20-50L/h.
The forming method of the invention is characterized in that the drying temperature of the gel pellets is preferably 60-120 ℃ and the drying time is preferably 6-24 hours; the roasting temperature is 400-1100 ℃, the roasting time is 2-12 hours, and the roasting medium is dry air or wet air with the water content below 5 wt%.
Compared with the prior art, the invention has the following advantages:
(1) According to the spherical carrier forming method provided by the invention, the alumina sol is dripped into the quasi-homogeneous phase forming oil formed by mixing ammonia gas and oil phase, so that the spherical carrier forming method is high in balling rate and good in forming effect.
(2) The forming equipment forms closed loop circulation, has good sealing, no liquid or gas leakage and good environmental protection effect.
(3) The forming process is maintained at normal temperature, so that the energy consumption is saved, and the reduction of the balling efficiency caused by the deterioration of the oil phase can be avoided.
(4) The forming process can realize continuous operation, is simple and is easy to realize industrialization.
Drawings
Fig. 1 is a schematic structural view of a spherical carrier molding apparatus of the present invention.
In the figure, 1, a ball dropping disc, 2, a ball valve, 3, a disperser, 4 ammonia gas pipelines, 5 oil phase pipelines, 6, a pump, 7, a ball column, 8, a quasi-homogeneous organic phase, 9, a dryer, 10, a ball valve, 11 and a sewage pipeline.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The method for forming the alumina drip ball provided by the invention comprises the following steps:
mixing hydrated alumina powder with water to prepare alumina suspension, stirring, adding an acid solution to acidify and peptize alumina to form alumina sol, pouring the alumina sol into a spherical carrier molding device to form spherical gel particles, taking out, aging in an ammonia water solution, drying and roasting to obtain the spherical alumina carrier.
Referring to the spherical carrier forming device shown in fig. 1, the spherical carrier forming device comprises a ball dropping disc 1, a ball forming column 7 and a dryer 9 which are sequentially connected from top to bottom, wherein the bottom of the ball forming column 7 is communicated with a premixing device, and upper ammonia gas and a lower organic phase 8 are stored in the ball forming column 7, wherein the organic phase is the quasi-homogeneous organic solution. The forming device forms closed loop circulation, has good sealing, no liquid or gas leakage and good environmental protection effect.
The premixing device comprises an ammonia gas pipeline 4, an oil phase pipeline 5 and a disperser 3, wherein the ammonia gas pipeline 4 and the oil phase pipeline 5 are connected in parallel to the disperser 3 through a micro-regulator (not shown), the disperser 3 is connected with the lower part of a balling column 7, and upper ammonia gas and a lower organic phase 8 in the balling column 7 are respectively circulated into the disperser 3 through a ball valve 2 and a pump 6; a drain outlet (not shown) is arranged at the bottom of the dryer 9 and is communicated with a drain pipeline 11, and a ball valve 10 is arranged on the drain pipeline 11.
The molding process comprises the following steps: introducing alumina sol into a ball drop tray 1 of a forming device, then dripping the alumina sol into a ball forming column 7, shrinking the ball forming column 7 under the action of an oil phase in the ball forming column, and solidifying the alumina sol under the action of ammonia dissolved in an organic solvent to form gel pellets; the organic solvent is circulated into the disperser by a pump in the dripping process to be remixed with the ammonia gas, and the ammonia gas lost by the system is replenished by an ammonia gas pipeline. In the dropping process, the dropping speed is 1-2 kg/h by a pseudo-boehmite mass meter, the circulation ratio of the pump is 0-0.20, and the ammonia flow of the ammonia pipeline is 20-50L/h.
Specifically, the dropping process is continuous operation, the alumina sol forms liquid drops through the dropping ball disc, the liquid drops enter a water-insoluble quasi-homogeneous organic solvent in a ball column through the action of gravity, shrink into balls under the action of surface tension, and meanwhile, the liquid drops are solidified into gel balls through neutralization reaction with NH 3 dissolved in the solvent. And the organic solvent is circulated into the disperser by a pump to be remixed with NH 3 in the process of dripping, the circulation ratio is 0-0.2 (reflux quantity/quantity of organic phase in the forming column), and the circulation quantity depends on the dripping speed, the acid aluminum ratio and the solubility of different solvents to NH 3. And opening an ammonia pipeline to supplement NH 3 lost by the system, wherein the flow rate of the ammonia is 20-50L/h.
Measurement method
Bulk density: taking a certain mass of sample, filling the sample into a 250mL measuring cylinder, piling the sample after certain vibration and tapping, and reading the volume value. The bulk density of the sample is the ratio of mass/volume at this time.
Specific surface area: the specific surface areas of the catalyst and the support were measured by the nitrogen adsorption BET method. The degassed catalyst sample adsorbs nitrogen at low temperature, when adsorption reaches equilibrium, equilibrium adsorption pressure and adsorbed gas amount are measured, and the adsorption amount of a sample monolayer is calculated according to a BET equation, so that the specific surface area of the sample is calculated. Reference standard ASTM D3663.
Crush strength: and placing the catalyst particles on a measuring table of a particle strength tester, applying gradually increasing pressure until the catalyst is crushed, wherein the pressure at the moment is the crushing strength, repeatedly measuring for 20-30 times, and taking an average value to obtain the average crushing strength. Reference standard ASTM D4179.
Pore volume: the pore volume of the sample was measured using nitrogen adsorption, reference standard ASTM D4222. Mercury intrusion method, standard ASTM D4284.
Pore diameter: the nitrogen desorption isotherm calculation was used, with reference to standard SH/T0572.
Crystalline phase: the crystal structure of the samples was analyzed by X-ray diffraction (XRD).
Example 1
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.4kg of deionized water to stir for 30min for pulping, and adding 173g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution to obtain alumina sol with the solid content of alumina of 21wt% and the molar ratio of H +/Al3+ of 0.07.
(2) And (3) forming: the catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser and enters a molding column 7, and the solvent in the molding column 7 begins to drip after 80-90% (volume) of the solvent is filled. The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the forming column 7 to the disperser 3 for remixing, while the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.08, and the ammonia gas input flow rate was 23L/h. After the completion of the dripping, shaped gel particles are obtained in a dryer 9.
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, aging in ammonia water solution (with concentration of 8wt%) for 10h, drying at 80deg.C for 12h, respectively roasting at 650deg.C and 950deg.C for 4h, wherein the roasting medium is dry air, to obtain alumina solid pellets 1A and 1B, and the physical parameters are shown in Table 1.
Example 2
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 1.9kg of deionized water to stir for 30min for pulping, and adding 173g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution to obtain alumina sol with the solid content of alumina of 25wt% and the molar ratio of H +/Al3+ of 0.07.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the solvent in the molding column begins to drip after the solvent is filled to 80-90% (volume). The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.08, and the ammonia gas input flow rate was 23L/h. After the completion of the dripping, shaped gel particles are obtained in a dryer 9.
(3) The subsequent processing method comprises the following steps: the molded gel particles were taken out and put into an aqueous ammonia solution (the concentration is the same as above) to age for 10 hours, dried at 80 ℃ for 12 hours, and baked at 650 ℃ for 4 hours, wherein the baking mediums are dry air and air containing 3wt% of water respectively, and the alumina solid pellets 2A and 2B are obtained, and the physical parameters are shown in Table 1.
Example 3
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.1kg of deionized water to stir for 30min for pulping, and adding 148g of nitric acid solution with the mass concentration of 37.5wt% to peptize the mixture to obtain alumina sol with the solid content of 23wt% and the molar ratio of H +/Al3+ of 0.06.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the solvent in the molding column begins to drip after the solvent is filled to 80-90% (volume). The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.07, and the ammonia gas input flow rate was 20L/h.
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, placing the gel particles in an aging solution (the concentration is the same as the above) in ammonia water for 10h, drying the gel particles at 80 ℃ for 12h, and roasting the gel particles at 750 ℃ for 4h, wherein a roasting medium is dry air, so that alumina solid pellets 3 are obtained, and the physical parameters are shown in table 1.
Example 4
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 1.5kg of deionized water to stir for 30min for pulping, and adding 148g of nitric acid solution with the mass concentration of 37.5wt% to peptize the mixture to obtain alumina sol with the solid content of alumina of 28wt% and the molar ratio of H +/Al3+ of 0.06.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the dripping is started after the solvent in the molding column is filled to 80-90%. The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.07, and the ammonia gas input flow rate was 20L/h.
(3) The subsequent processing method comprises the following steps: the gel particles after molding were taken out and put into an aqueous ammonia solution (the concentration is the same as above) to age for 10 hours, dried at 80 ℃ for 12 hours, and baked at 650 ℃ for 4 hours, wherein the baking mediums are dry air and air containing 3wt% of water respectively, and the physical parameters of the alumina solid pellets 4 are shown in table 1.
Example 5
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 1.7kg of deionized water to stir for 30min for pulping, and adding 222g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution to obtain alumina sol with the solid content of alumina of 26wt% and the molar ratio of H +/Al3+ of 0.09.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the dripping is started after the solvent in the molding column is filled to 80-90%. The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.1, and the ammonia gas input flow rate was 30L/h.
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, aging in ammonia water solution (with the same concentration as above) for 10h, drying at 80 ℃ for 12h, and roasting at 650 ℃ and 1050 ℃ for 4h respectively, wherein the roasting medium is dry air, so as to obtain alumina solid pellets 5A and 5B, and the physical parameters are shown in table 1.
Example 6
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 1.9kg of deionized water to stir for 30min for pulping, and adding 197g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution, thus obtaining alumina sol with the solid content of alumina of 24wt% and the molar ratio of H +/Al3+ of 0.08.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-octane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-octane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-octane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the dripping is started after the solvent in the molding column is filled to 80-90%. The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-octane gas in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-octane recycle ratio (reflux amount/amount of organic phase in the molding column) was 0.09, and the ammonia gas input amount was 26L/h.
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, aging in ammonia water solution (with the same concentration as above) for 10 hours, drying at 80 ℃ for 12 hours, and roasting the gel particles at 650 ℃ with dry air as a medium to obtain alumina solid pellets 6, wherein the physical parameters are shown in table 1.
Example 7
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.1kg of deionized water to stir for 30min for pulping, and adding 173g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution to obtain alumina sol with the solid content of alumina of 23wt% and the molar ratio of H +/Al3+ of 0.07.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the dripping is started after the solvent in the molding column is filled to 80-90%. The dropping speed was 1.5kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane gas in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.11, and the ammonia gas input amount was 35L/h.
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, aging in ammonia water solution (with the same concentration as above) for 10h, drying at 80 ℃ for 12h, roasting at 750 ℃ for 4h, and taking the roasting medium as dry air to obtain alumina solid pellets 7, wherein the physical parameters are shown in table 1.
Example 8
(1) Preparing alumina sol: 0.15kg of boehmite powder (the dry basis content of alumina is 85 wt%) and 0.85kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) are taken, 2.3kg of deionized water is added, stirring is carried out for 30min for pulping, 174g of nitric acid solution with the mass concentration of 37.5wt% is added for peptizing, and alumina sol with the solid content of alumina of 22wt% and the molar ratio of H +/Al3+ of 0.07 is obtained.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the dripping is started after the solvent in the molding column is filled to 80-90%. The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.08, and the ammonia gas input amount was 24L/h. .
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, aging in ammonia water solution (with the same concentration as above) for 10h, drying at 80 ℃ for 12h, and roasting at 650 ℃ for 4h, wherein the roasting medium is dry air, so as to obtain alumina solid pellets 8, and the physical parameters are shown in table 1.
Example 9
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.1kg of deionized water to stir for 30min for pulping, and adding 148g of nitric acid solution with the mass concentration of 37.5wt% to peptize the mixture to obtain alumina sol with the solid content of 23wt% and the molar ratio of H +/Al3+ of 0.06.
(2) And (3) forming: according to the novel catalyst spherical carrier forming device shown in the figure 1, cyclohexane is selected as an organic solvent required by forming, the input flow rates of ammonia gas and cyclohexane are respectively 15L/min and 800g/min, a disperser is fully mixed to form a quasi-homogeneous mixed solvent, the quasi-homogeneous mixed solvent enters a forming column 7, and after the solvent in the forming column is filled to 80-90%, the forming column begins to drip balls. The dropping speed was 1.2kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower cyclohexane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The cyclohexane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.06, and the ammonia gas input flow rate was 24L/h.
(3) The subsequent processing method comprises the following steps: taking out the formed gel particles, aging in ammonia water solution (with the same concentration as above) for 10 hours, drying at 80 ℃ for 12 hours, and roasting the gel particles at 650 ℃ with dry air as a medium to obtain alumina solid pellets 9, wherein the physical parameters are shown in table 1.
Comparative example 1
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.2kg of deionized water to stir for 30min for pulping, and adding 98g of nitric acid solution with the mass concentration of 37.5wt% to peptize the mixture to obtain alumina sol with the solid content of 23wt% and the molar ratio of H +/Al3+ of 0.04.
(2) And (3) forming: the novel catalyst spherical carrier molding device shown in the figure 1 is adopted, n-heptane is selected as an organic solvent required by molding, the input flow rates of ammonia gas and n-heptane are respectively 15L/min and 800g/min, a quasi-homogeneous mixed solvent is formed after the ammonia gas and the n-heptane are fully mixed in a disperser, the mixed solvent enters a molding column 7, and the dripping is started after the solvent in the molding column is filled to 80-90%. The dropping speed was 1kg/h (based on the mass of pseudo-boehmite powder), and during the dropping, the valve 2 and the pump 6 were opened to circulate the upper ammonia gas and the lower n-heptane in the molding column to the disperser for remixing, and at the same time, the ammonia gas input line was opened to replenish the ammonia lost in the system. The n-heptane circulation ratio (reflux amount/amount of organic phase in the molding column) was 0.047, and the ammonia gas input amount was 14L/h.
(3) The subsequent processing method comprises the following steps: the gel particles after molding were taken out and put into an aqueous ammonia solution (the concentration is the same as in example 1) to age for 10 hours, dried at 80 ℃ for 12 hours, and baked at 650 ℃ for 4 hours, wherein the baking medium is dry air, and the alumina solid pellets I are obtained, and the physical parameters are shown in Table 1.
Comparative example 2
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.1kg of deionized water to stir for 30min for pulping, and adding 173g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution to obtain alumina sol with the solid content of alumina of 23wt% and the molar ratio of H +/Al3+ of 0.07.
(2) And (3) forming: the alumina sol is dripped into an oil ammonia column with the concentration of 8wt% of ammonia water at the upper layer and the concentration of ammonia water at the lower layer, wherein the height of the n-heptane is 10cm, the height of the ammonia water is 80cm, the formed pellets are aged for 12 hours in an ammonia water solution (the concentration is the same as that of example 1), the pellets are taken out and washed by deionized water, dried for 12 hours at 80 ℃, baked for 4 hours at 650 ℃, and the baked medium is dry air, so that the alumina solid pellets II are obtained, and the physical parameters of the pellets are shown in table 1.
Comparative example 3
(1) Preparing alumina sol: taking 1kg of pseudo-boehmite powder (the dry basis content of alumina is 75 wt%) and adding 2.1kg of deionized water to stir for 30min for pulping, and adding 173g of nitric acid solution with the mass concentration of 37.5wt% to peptize the solution to obtain alumina sol with the solid content of alumina of 23wt% and the molar ratio of H +/Al3+ of 0.07.
And (3) forming: mixing alumina sol and 260g of hexamethylene tetramine solution with the mass concentration of 35wt%, stirring for 30min, dripping into a hot oil molding column filled with white oil, aging the molded wet balls in hot oil at the oil bath temperature of 96 ℃ for 6h, taking out from the hot oil, and aging in an ammonia water solution (the concentration is the same as that of example 1) for 10h to solidify the wet balls. Washing the aged pellets with ionized water, drying at 80 ℃ for 12h, and roasting at 650 ℃ for 4h, wherein a roasting medium is dry air, so that the alumina solid pellets III are obtained, and the physical parameters are shown in table 1.
TABLE 1
As can be seen from Table 1, the specific surface area, strength, pore structure and other properties of the alumina pellets prepared by the method of the invention are equivalent to those of alumina pellets prepared by an oil-ammonia method and hot oil column fermentation, and can meet the index requirements required by reforming catalyst carriers. In the forming process, the solid content of alumina sol, the acid-aluminum ratio and other parameters can be adjusted according to the requirement to obtain alumina pellets with specific bulk density so as to adapt to different catalytic reaction process conditions.
The method realizes the closed circulation of ammonia gas, ensures the green and pollution-free forming process, has high balling rate and good forming effect, can realize the continuous operation of catalyst forming, has simple and easy operation process and has good application prospect.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (15)
1. A method for forming spherical alumina, comprising the steps of:
(1) Mixing hydrated alumina with deionized water to obtain a suspension, stirring, and adding an acid solution to carry out peptization to obtain alumina sol;
(2) Dripping the alumina sol prepared in the step (1) into a forming device for forming, wherein the forming liquid is a quasi-homogeneous organic solution formed by fully mixing ammonia gas and an oil phase, taking out formed pellets, and aging, drying and roasting to obtain a spherical alumina carrier;
The forming device comprises a ball dropping disc, a ball forming column and a dryer which are sequentially connected from top to bottom, wherein the bottom of the ball forming column is communicated with the premixing device, and upper ammonia gas and lower organic phases are stored in the ball forming column, wherein the organic phases are the quasi-homogeneous organic solution.
2. The molding method of claim 1, wherein the hydrated alumina is boehmite, pseudo-boehmite, or a mixture of both.
3. The molding method as claimed in claim 1, wherein the solid content of the suspension in step (1) is 20 to 40% by weight based on the mass of alumina.
4. The molding method according to claim 1, wherein the solid content of the alumina sol is 10 to 30wt% in terms of alumina.
5. The molding method according to claim 1, wherein the aging is performed in an aqueous ammonia solution having a concentration of 6 to 10wt%, and the aging is performed for 1 to 12 hours at a temperature of 20 to 40 ℃.
6. The molding method according to claim 1, wherein the acid in the acid solution is nitric acid, hydrochloric acid, formic acid, acetic acid or perchloric acid, the mass concentration of the acid solution is 5-50 wt%, and the amount of the acid solution is 0.04-0.1 in terms of H +/Al3+ molar ratio in the alumina sol.
7. The molding method as claimed in claim 6, wherein the acid in the acid solution is nitric acid or hydrochloric acid.
8. The molding method according to claim 1, wherein the oil phase in the quasi-homogeneous organic solution is at least one of heptane, octane, nonane, gasoline, kerosene, paraffin oil, mineral oil, petroleum ether.
9. The molding method as claimed in claim 1, wherein the premixing device comprises an ammonia gas line, an oil phase line and a disperser, the ammonia gas line and the oil phase line are connected in parallel to the disperser through a micro-regulator, the disperser is connected with a ball column, and upper ammonia gas and lower organic phase in the ball column are circulated into the disperser through a ball valve and a pump, respectively.
10. The molding method of claim 9, wherein the disperser is made of ceramic, metal, or film material.
11. The molding method of claim 9, wherein the pump is a diaphragm pump, a slurry pump, a plunger pump, or a water pump.
12. The molding method of claim 1, wherein a drain is provided at the bottom of the dryer.
13. The molding method according to claim 9, wherein the molding process comprises the steps of: introducing alumina sol into the ball-dropping disc of the forming device, then dripping the alumina sol into the ball-dropping column, shrinking the ball-dropping column to form balls under the action of oil phase in the ball-dropping column, and solidifying the balls under the action of ammonia dissolved in an organic solvent to form gel balls; and in the dripping process, the organic solvent is circulated into the disperser through a pump to be remixed with the ammonia gas, and the ammonia gas lost by the system is replenished through an ammonia gas pipeline.
14. The molding method as claimed in claim 13, wherein the dropping speed is 1 to 2kg/h, the circulation ratio of the pump is 0 to 0.20, and the flow rate of the ammonia gas in the ammonia gas line is 20 to 50L/h.
15. The molding method according to claim 13, wherein the gel pellets are dried at 60 to 120 ℃ for 6 to 24 hours; the roasting temperature is 400-1100 ℃, the roasting time is 2-12 hours, and the roasting medium is dry air or wet air with the water content below 5 wt%.
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