CN114835135B - A titanium-containing gas-phase ultrastable mesoporous Y zeolite and its preparation method and application - Google Patents
A titanium-containing gas-phase ultrastable mesoporous Y zeolite and its preparation method and application Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 210
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 209
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 200
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010936 titanium Substances 0.000 title claims abstract description 56
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 76
- 239000007789 gas Substances 0.000 claims description 74
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 238000010926 purge Methods 0.000 claims description 17
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
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- 230000002378 acidificating effect Effects 0.000 claims description 3
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- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 21
- 239000003921 oil Substances 0.000 abstract description 12
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 53
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 21
- 239000005049 silicon tetrachloride Substances 0.000 description 21
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- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 238000005336 cracking Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
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- 230000001502 supplementing effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
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- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- -1 ZSM-5 Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
本发明提供了一种含钛的气相超稳介孔Y沸石及其制备方法与应用，该制备方法包括如下步骤：步骤1，将微孔NaY沸石与四氯化钛气体进行气固反应，反应温度为350～550℃，反应时间为10～240分钟；以及步骤2，将步骤1反应后的NaY沸石经去离子水洗涤、过滤、干燥，得到含钛的气相超稳介孔Y沸石。本发明方法制备的Y沸石具有较为丰富的介孔结构、酸性适宜、钛硅比可控，所得Y沸石制备的催化裂化催化剂具有较好的增加重质油转化和提高轻质油产率的能力。
The present invention provides a titanium-containing gas-phase ultra-stable mesoporous Y zeolite and a preparation method and application thereof, the preparation method comprising the following steps: step 1, subjecting microporous NaY zeolite to a gas-solid reaction with titanium tetrachloride gas, the reaction temperature being 350-550°C, and the reaction time being 10-240 minutes; and step 2, washing, filtering, and drying the NaY zeolite after the reaction in step 1 with deionized water to obtain a titanium-containing gas-phase ultra-stable mesoporous Y zeolite. The Y zeolite prepared by the method of the present invention has a relatively rich mesoporous structure, suitable acidity, and a controllable titanium-silicon ratio. The catalytic cracking catalyst prepared from the obtained Y zeolite has a good ability to increase the conversion of heavy oil and improve the yield of light oil.
Description
Technical Field
The invention relates to the field of zeolite catalysts, in particular to a gas-phase ultrastable mesoporous Y zeolite containing titanium, a preparation method of the gas-phase ultrastable mesoporous Y zeolite containing titanium and application of the gas-phase ultrastable mesoporous Y zeolite containing titanium.
Background
Catalytic cracking processes are important secondary processing processes for crude oil. Therefore, the catalytic cracking process is very important in increasing the yield of light oil in heavy oil processing, wherein the importance of the catalytic cracking catalyst and the main active component Y-type zeolite thereof is self-evident. The product distribution of the catalytic cracking reaction is mainly determined by the cracking activity and selectivity of the Y-type zeolite, and the influence of the properties of the zeolite such as silicon-aluminum ratio, pore structure, crystallinity, acid distribution and the like on the catalytic cracking performance is always the focus of research and development in the field.
In recent years, the degree of heavy and poor quality of crude oil at home and abroad is increasing, and the demands for light oil in daily life are increasing. In order to improve the capability of deep processing of catalytic cracking of heavy feedstock, the requirements of the oil refining industry on FCC catalysts are also increasing, and the Y-type zeolite as an active component is therefore required to perfect its modification method to be better suited for catalytic cracking processes.
Y-type zeolite is widely used in catalytic cracking reactions because of its suitable acid properties, extremely high specific surface area and excellent thermal stability. However, the microporous structure of the Y-zeolite severely impedes the diffusion of heavy oil macromolecules within the pores, resulting in poor accessibility of the acidic active sites thereof, reducing the catalytic performance of the Y-zeolite as the active component of the catalyst. In order to improve the cracking ability of the Y-type zeolite to heavy and poor quality raw oil, a mesoporous structure needs to be introduced into the Y-type zeolite to improve the diffusion rate of heavy oil macromolecules in pores and improve the accessibility of acid active centers. It can be seen that the Y-zeolite with mesoporous structure is very suitable for catalytic cracking of heavy oil, and it affects the product distribution and economic benefits of the catalytic cracker.
Existing methods for preparing mesoporous Y-type zeolite are largely divided into two categories, namely direct synthesis and post-modification treatment. Three main methods for obtaining mesoporous through post-treatment modification are hydrothermal method, alkali treatment method and acid-alkali coupling treatment method.
The organic template agent is used in the direct synthesis process, and the obtained Y-type zeolite has regular and ordered mesopores and obviously increased volume and external specific surface area. However, expensive organic templates greatly increase the production cost of zeolite, so that there are problems in terms of high cost and environmental pollution for large-scale industrial production.
Hydrothermal treatment has been developed in the last 60 th century. The method takes directly synthesized NaY zeolite as a treatment object, and the NaY zeolite is baked at high temperature in a water vapor atmosphere after ammonium exchange. The process is repeated twice or even more times, the mesoporous structure can be obtained while the silicon-aluminum ratio of the zeolite framework is improved, and the Y-type zeolite obtained by the method is called USY-type zeolite. However, such a method generally requires two or more times of ammonium ion exchange and hydrothermal treatment, and is high in energy consumption and high in ammonium salt consumption.
In 1980 Beyer firstly proposed a method for dealuminating silicon tetrachloride in gas phase and supplementing silicon, generally SiCl 4 under the protection of nitrogen is adopted to react with dehydrated Y-type zeolite at a certain temperature, and SiCl 4 is inserted into silicon in silicon tetrachloride while removing framework aluminum, so as to finish dealuminating and supplementing silicon. The high-silicon zeolite obtained by the method can effectively avoid hydroxyl holes generated when the Y-type zeolite is subjected to dealumination and silicon supplementing reaction under the hydrothermal condition, and avoid the defects of lattice collapse and structure damage, so that the zeolite with high crystallization retention degree and high thermal stability can be prepared.
The mesoporous structure is manufactured by an alkali treatment method and an acid-alkali coupling treatment method on the basis that SiCl 4 improves the silicon-aluminum ratio of the Y-type zeolite framework, and the flow is relatively long.
The newly developed alkaline treatment process in recent years is effective in reproducing mesopores, however, the process is suitable for use with high silica to alumina ratio zeolites (e.g., ZSM-5, silica to alumina mole ratio 25). In the case of an aluminum-rich Y-type zeolite, if such a method is to be used, the framework silica-alumina ratio of the zeolite must be increased. Patent CN104843736a is a process for preparing Y-type zeolite containing mesoporous structure. Patent CN104760973a uses an acid-base coupling treatment method to prepare Y-type zeolite containing ultra-high mesoporous content. Compared with a hydrothermal method, the method obviously shortens the flow and obviously reduces the energy consumption. However, three steps are still required to obtain mesoporous Y zeolite, namely, gas-phase ultrastable silicon tetrachloride of NaY, acid treatment and alkali treatment.
In view of the foregoing, there is still a lack of technology in the art for preparing mesoporous Y zeolite featuring low cost, low energy consumption, short process, and short time.
Disclosure of Invention
The invention mainly aims to provide a gas-phase ultrastable mesoporous Y zeolite containing titanium, and a preparation method and application thereof, so as to solve the defects of high preparation cost, complex process, long time consumption and the like of the mesoporous Y zeolite in the prior art.
In order to achieve the above purpose, the invention provides a preparation method of a gas-phase ultrastable mesoporous Y zeolite containing titanium, which comprises the following steps:
Step 1, carrying out gas-solid reaction on microporous NaY zeolite and titanium tetrachloride gas, wherein the reaction temperature is 350-550 ℃ and the reaction time is 10-240 minutes, and
And 2, washing, filtering and drying the NaY zeolite reacted in the step 1 by deionized water to obtain the gas-phase ultrastable mesoporous Y zeolite containing titanium.
The preparation method of the titanium-containing gas-phase ultrastable mesoporous Y zeolite comprises the steps of calculating the silicon-aluminum molar ratio of the microporous NaY zeolite to be 4.5-5.5 in terms of the molar ratio of SiO 2 to Al 2O3, wherein the dry basis Na 2 O content of the microporous NaY zeolite is 11-14wt%, the total pore volume of the microporous NaY zeolite is not less than 0.250cm 3/g, and the BET specific surface area is not less than 550m 2/g.
The invention relates to a preparation method of a gas-phase ultrastable mesoporous Y zeolite containing titanium, wherein the microporous NaY zeolite contains rare earth elements, the content of the rare earth elements is 1-10wt% based on RE 2O3, the content of Na 2 O is not less than 5wt%, and/or the rare earth elements are one or two of lanthanum and cerium.
The invention relates to a preparation method of a gas-phase ultrastable mesoporous Y zeolite containing titanium, wherein the preparation method further comprises the step of drying the microporous NaY zeolite before the microporous NaY zeolite and titanium tetrachloride gas undergo a gas-solid reaction.
The invention relates to a preparation method of a titanium-containing gas-phase ultrastable mesoporous Y zeolite, wherein titanium tetrachloride gas is introduced into the microporous NaY zeolite to carry out gas-solid reaction under the carrying of dry gas, and the dry gas is one, two or more than two of the group consisting of nitrogen, air, argon and helium.
The invention relates to a preparation method of a titanium-containing gas-phase ultrastable mesoporous Y zeolite, wherein the mass ratio of titanium tetrachloride gas to microporous NaY zeolite dry basis is 0.1-0.8:1.
According to the preparation method of the titanium-containing gas-phase ultrastable mesoporous Y zeolite, silicon tetrachloride gas is mixed in the titanium tetrachloride gas, the mass ratio of the titanium tetrachloride gas to the silicon tetrachloride gas is not less than 4:1, and the mass ratio of the sum of the titanium tetrachloride gas and the silicon tetrachloride gas to the micropore NaY zeolite dry basis is 0.1-0.8:1.
The preparation method of the titanium-containing gas-phase ultrastable mesoporous Y zeolite comprises a stage of performing gas-solid reaction between microporous NaY zeolite and titanium tetrachloride gas and a reaction stage of stopping adding titanium tetrachloride gas after the microporous NaY zeolite and the titanium tetrachloride gas are subjected to gas-solid reaction.
The invention relates to a preparation method of a titanium-containing gas-phase ultrastable mesoporous Y zeolite, wherein the reacted NaY zeolite is washed by deionized water, and the mass ratio of the NaY zeolite to the deionized water is 1:5-10.
In order to achieve the aim, the invention also provides the titanium-containing gas-phase ultrastable mesoporous Y zeolite obtained by the preparation method of the titanium-containing gas-phase ultrastable mesoporous Y zeolite.
The gas-phase ultrastable mesoporous Y zeolite containing titanium, provided by the invention, has a total pore volume of 0.324-0.376cm 3/g, a mesoporous volume of 0.079-0.197cm 3/g and a mesoporous volume accounting for 21.0-60.8% of the total pore volume.
In order to achieve the aim, the invention further provides application of the titanium-containing gas-phase ultrastable mesoporous Y zeolite as an acidic active component of a catalytic cracking catalyst.
The invention has the beneficial effects that:
The invention introduces considerable mesoporous and hetero atom titanium into Y-type zeolite through simple process, and simultaneously retains more acid centers of Y-type zeolite. Compared with the existing method for preparing mesoporous Y-type zeolite, the method shortens the reaction flow, reduces the reaction time, reduces the energy consumption and can save the production cost. And the heavy oil conversion capability of the FCC catalyst prepared by taking the Y-type zeolite as an active component is enhanced, and the yield of light oil is improved.
Drawings
FIG. 1 shows XRD patterns of Y zeolite obtained in examples 1,5 and 6 of the present invention.
Detailed Description
The following describes 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 scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention provides a preparation method of a gas-phase ultrastable mesoporous Y zeolite containing titanium, which comprises the following steps:
Step 1, carrying out gas-solid reaction on microporous NaY zeolite and titanium tetrachloride gas, wherein the reaction temperature is 350-550 ℃ and the reaction time is 10-240 minutes, and
And 2, washing, filtering and drying the NaY zeolite reacted in the step 1 by deionized water to obtain the gas-phase ultrastable mesoporous Y zeolite containing titanium.
The technical scheme of the invention is mainly used for modifying the microporous NaY zeolite to prepare the NaY zeolite with rich mesoporous structure. The preparation method of the microporous NaY zeolite is not particularly limited in the present invention, and the conventional preparation method of the microporous NaY zeolite in the art may be used. As an optimal technical scheme, the silicon-aluminum molar ratio of the microporous NaY zeolite is 4.5-5.5, preferably 4.8-5.3:1, calculated by the molar ratio of SiO 2 to Al 2O3. The dry basis Na 2 O content of the microporous NaY zeolite is preferably 11-14wt%, the total pore volume of the microporous NaY zeolite is preferably not less than 0.250cm 3/g, the BET specific surface area is preferably not less than 550m 2/g, the total pore volume of the NaY zeolite is further preferably not less than 0.300cm 3/g, and the BET specific surface area is further preferably not less than 650m 2/g. Wherein, the dry basis Na 2 O content of the microporous NaY zeolite refers to the content of Na 2 O based on the dry basis of the microporous NaY zeolite.
As a preferable technical scheme, the microporous NaY zeolite can also contain rare earth elements, wherein the content of the rare earth elements in terms of RE 2O3 is 1-10wt% and the content of Na 2 O is not less than 5wt%. The rare earth element may be one or two of lanthanum and cerium, but the invention is not limited thereto. The dry basis rare earth element content of the microporous NaY zeolite refers to the content of the rare earth element calculated by RE 2O3 based on the dry basis of the microporous NaY zeolite.
In addition, according to a preferred embodiment of the present invention, the microporous NaY zeolite or the rare earth-containing microporous NaY zeolite is subjected to a drying treatment before being subjected to a gas-solid reaction with titanium tetrachloride gas, and the sample is stored in a dry atmosphere environment to be reacted with titanium tetrachloride gas. In the drying treatment method of NaY zeolite or rare earth-containing NaY zeolite, the preferable treatment temperature is 400-550 ℃ and the treatment time is 60-120 minutes.
The operation of carrying out the gas-solid reaction between the microporous NaY zeolite and the titanium tetrachloride gas can be that the titanium tetrachloride gas is introduced into the microporous NaY zeolite under the condition of carrying the drying gas, and the gas-solid reaction is carried out under the anhydrous drying environment, wherein the preferable gas-solid reaction temperature is 400-550 ℃, and the preferable gas-solid reaction time is 60-120 minutes. The drying gas may be one, two or a combination of more than two of the group consisting of nitrogen, air, argon and helium. The mass ratio of titanium tetrachloride gas to the microporous NaY zeolite dry basis is 0.1-0.8:1.
In another embodiment of the invention, the microporous NaY zeolite is subjected to gas-solid reaction with the mixed gas of titanium tetrachloride and silicon tetrachloride, namely, the mixed gas of titanium tetrachloride and silicon tetrachloride is introduced into the microporous NaY zeolite under the carrying of dry gas, and the gas-solid reaction is carried out in an anhydrous dry environment. The mass ratio of the titanium tetrachloride gas to the silicon tetrachloride gas is preferably not less than 4:1, and the mass ratio of the sum of the titanium tetrachloride gas and the silicon tetrachloride gas to the micropore NaY zeolite dry basis is 0.1-0.8:1.
In the present invention, the ratio of the titanium tetrachloride gas or the mixed gas of titanium tetrachloride and silicon tetrachloride to the drying gas is preferably such that the titanium tetrachloride gas or the mixed gas of titanium tetrachloride and silicon tetrachloride is saturated in the drying gas.
The gas-solid reaction of the microporous NaY zeolite and titanium tetrachloride gas or titanium tetrachloride and silicon tetrachloride mixed gas comprises a gas-solid reaction stage of the microporous NaY zeolite and continuously introduced titanium tetrachloride gas or titanium tetrachloride and silicon tetrachloride mixed gas and a reaction stage of the microporous NaY zeolite under the purging of dry gas after the introduction of the titanium tetrachloride gas or the titanium tetrachloride and silicon tetrachloride mixed gas is stopped. That is, the titanium tetrachloride gas or the mixed gas of titanium tetrachloride and silicon tetrachloride is continuously introduced into the microporous NaY zeolite for reaction for a period of time, then the introduction of the titanium tetrachloride gas or the mixed gas of titanium tetrachloride and silicon tetrachloride is stopped, and the microporous NaY zeolite is continuously reacted for a period of time under the condition that only the dry gas is continuously introduced, so that the microporous NaY zeolite can be fully reacted, and the agglomeration of the NaY zeolite can be prevented.
In one embodiment, the reaction time is 10-240 minutes, including the time of the gas-solid reaction stage of the microporous NaY zeolite and the continuously introduced titanium tetrachloride gas or the mixed gas of titanium tetrachloride and silicon tetrachloride, and the time of the reaction stage of the microporous NaY zeolite under the purging of the dry gas after stopping the introduction of the titanium tetrachloride gas or the mixed gas of titanium tetrachloride and silicon tetrachloride.
Washing, filtering and drying the reacted NaY zeolite by deionized water to obtain the gas-phase ultrastable mesoporous Y zeolite containing titanium. The mass ratio of the NaY zeolite to the deionized water is preferably 1:5-10. The drying temperature and drying time are not particularly limited in the present invention, and are, for example, 80 to 120 ℃ overnight.
The total pore volume of the gas-phase ultrastable mesoporous Y zeolite containing titanium obtained by the method is 0.324-0. 3 cm/g, the mesoporous volume is 0.079-0.197cm 3/g, and the proportion of the mesoporous volume to the total pore volume is 21.0-61.0%.
The preparation method not only avoids the defect of high price of the template agent required by directly synthesizing the mesoporous Y zeolite, realizes the transformation from the microporous Y zeolite to the mesoporous Y zeolite by one-step operation, but also introduces heteroatom titanium into the Y zeolite phase at the same time, and further improves the cracking performance of the zeolite. In addition, the mesoporous Y zeolite obtained by the method has lower silicon-aluminum ratio, more acid centers are still reserved, the heavy oil conversion capability of the FCC catalyst prepared by taking the mesoporous Y zeolite as an active component is enhanced, and the yield of light oil is improved.
In order to make the technical features, objects and advantageous effects of the present invention more clearly understood, the technical solution of the present invention will be further described with specific embodiments.
In each example, the relative crystallinity and silica-alumina ratio of the Y-type zeolite prepared were measured as follows:
The sample crystallinity (relative crystallinity) was calculated using an X-ray powder diffractometer under the test conditions of CuK alpha radiation, ni filtering, tube voltage of 30kV, tube current of 40Ma, step width of 0.02, and the sum of the areas of eight peaks (compared with NaY zeolite standard) of (331), (511/333), (440), (533), (642), (822, 660), (555, 751), (664). The Si/Al ratio was determined according to SH/T0339-92 standard method (see "chemical industry Standard Association", china Standard Press, 2000) and the unit cell constant was calculated according to the following formula:
Wherein alpha is the unit cell constant Lambda is u-K alpha 1, wavelength: (h 2+k2+l2) is the square sum of the X-ray diffraction indexes. The Si/Al= (25.858-alpha)/(alpha-24.191) and SiO 2、Al2O3 =2× (Si/Al) were calculated according to the formula Breck-Flanigen.
Example 1
The embodiment provides a gas-phase ultrastable mesoporous Y-type zeolite containing titanium, which is prepared by the following steps:
40.0g of overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The skeleton silicon-aluminum ratio is 5.1, na 2 O content is 13.8 wt%) is placed in quartz reaction tube, dried high-purity nitrogen gas is introduced, nitrogen purging rate is set to be 50ml/min (glass rotor flowmeter), heating program of tubular furnace reactor is set, heating is carried out from initial temperature 20 ℃ to 550 ℃ for 53min, then the temperature is kept for 180min, natural cooling is carried out to 450 ℃ and then constant temperature is kept, and high-purity nitrogen gas saturated by TiCl 4 is introduced, wherein titanium tetrachloride consumption is 6.0g, and contact time is 60min. Stopping introducing high-purity nitrogen saturated by TiCl 4 after the reaction is finished, continuing to purge the reactor with the high-purity nitrogen for 120min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a water bath at 90 ℃, carrying out suction filtration until filtrate is neutral, taking out a filter cake, and drying the filter cake in a 120 ℃ oven overnight. Finally, the gas phase ultrastable mesoporous Y-type zeolite containing titanium is obtained.
The Y-zeolite obtained in this example was characterized by the relevant tests, and the phase structure, texture properties, and elemental composition results are shown in table 1.
Example 2
The embodiment provides a gas-phase ultrastable mesoporous Y-type zeolite containing titanium, which is prepared by the following steps:
5.0g of an overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The skeleton silicon-aluminum ratio is 5.1, na 2 O content is 13.8wt%) is placed in quartz reaction tube, high-purity nitrogen is introduced, after leak detection is made, nitrogen purge rate is set to be 50ml/min (glass rotor flowmeter), heating program of tubular furnace reactor is set, heating is carried out from initial temperature 20 ℃ to 500 ℃ for 48min, then the temperature is kept for 60min, natural cooling is carried out to 500 ℃ and then constant temperature is kept, and high-purity nitrogen saturated by TiCl 4 is introduced, wherein titanium tetrachloride is used in an amount of 1.0g, and the contact time is 120min. Stopping introducing high-purity nitrogen saturated by TiCl 4 after the reaction is finished, continuing to purge the high-purity nitrogen for 120min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a water bath at 90 ℃, carrying out suction filtration until filtrate is neutral, taking out a filter cake, and drying overnight in a 120 ℃ oven. Finally, the gas phase ultrastable mesoporous Y-type zeolite containing titanium is obtained.
The Y-zeolite obtained in this example was characterized by the relevant tests, and the phase structure, texture properties, and elemental composition results are shown in table 1.
Example 3
The embodiment provides a gas-phase ultrastable mesoporous Y-type zeolite containing titanium, which is prepared by the following steps:
5.0g of an overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The skeleton silicon-aluminum ratio is 5.1, na 2 O content is 13.8wt%) is placed in quartz reaction tube, high-purity nitrogen is introduced, after leak detection is made, nitrogen purge rate is set to be 50ml/min (glass rotor flowmeter), heating program of tubular furnace reactor is set, heating is carried out from initial temperature 20 ℃ to 550 ℃ for 53min, then the temperature is kept for 90min, natural cooling is carried out to 410 ℃ and then constant temperature is kept, and high-purity nitrogen saturated by TiCl 4 is introduced, wherein titanium tetrachloride is used in an amount of 1.5g, and the contact time is 120min. Stopping introducing high-purity nitrogen saturated by TiCl 4 after the reaction is finished, continuing to purge the high-purity nitrogen for 60min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a water bath at 90 ℃, carrying out suction filtration until filtrate is neutral, taking out a filter cake, and drying the filter cake in a 120 ℃ oven overnight. Finally, the gas phase ultrastable mesoporous Y-type zeolite containing titanium is obtained.
The Y-zeolite obtained in this example was characterized by the relevant tests, and the phase structure, texture properties, and elemental composition results are shown in table 1.
Example 4
The embodiment provides a gas-phase ultrastable mesoporous Y-type zeolite containing titanium, which is prepared by the following steps:
5.0g of an overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The skeleton silicon-aluminum ratio is 5.1, na 2 O content is 13.8wt%) is placed in quartz reaction tube, high-purity nitrogen is introduced, after leak detection is made, nitrogen purge rate is set to be 50ml/min (glass rotor flowmeter), heating program of tubular furnace reactor is set, heating is carried out from initial temperature 20 ℃ to 550 ℃ for 53min, then the temperature is kept for 60min, natural cooling is carried out to 450 ℃ and then constant temperature is kept, and high-purity nitrogen saturated by TiCl 4 is introduced, wherein titanium tetrachloride consumption is 3.0g, and contact time is 120min. Stopping introducing high-purity nitrogen saturated by TiCl 4 after the reaction is finished, continuing to purge the high-purity nitrogen for 60min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a water bath at 90 ℃, carrying out suction filtration until filtrate is neutral, taking out a filter cake, and drying overnight in a 120 ℃ oven. Finally, the gas phase ultrastable mesoporous Y-type zeolite containing titanium is obtained.
The Y-zeolite obtained in this example was characterized by the relevant tests, and the phase structure, texture properties, and elemental composition results are shown in table 1.
Example 5
The embodiment provides a gas-phase ultrastable mesoporous Y-type zeolite containing titanium, which is prepared by the following steps:
40.0g of overnight dried RENaY zeolite (relative crystallinity 88% of RENaY zeolite, unit cell constant, supplied by catalyst works of petrochemical company, lanzhou) was weighed out The framework silicon-aluminum ratio is 5.1, the Na 2 O content is 4.54wt%, the La 2O3 content is 1.43wt% and the CeO 2 content is 1.21 wt%) is placed in a quartz reaction tube, high-purity nitrogen is introduced, after leak detection work is carried out, the nitrogen purging rate is set to be 50ml/min (glass rotameter), the heating program of the tubular furnace reactor is set, the tubular furnace reactor is kept for 60min after the initial temperature is heated to 550 ℃ for 53min, the temperature is kept constant after the initial temperature is naturally reduced to 500 ℃, and high-purity nitrogen saturated by TiCl 4 is introduced, wherein the titanium tetrachloride consumption is 5.0g, and the contact time is 60min. Stopping introducing high-purity nitrogen saturated by TiCl 4 after the reaction is finished, continuing to purge the high-purity nitrogen for 60min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a water bath at 90 ℃, carrying out suction filtration until filtrate is neutral, taking out a filter cake, and drying the filter cake in a 120 ℃ oven overnight. Finally, the gas phase ultrastable mesoporous Y-type zeolite containing titanium is obtained.
The Y-zeolite obtained in this example was characterized by the relevant tests, and the phase structure, texture properties, and elemental composition results are shown in table 1.
Example 6
The embodiment provides a gas-phase ultrastable mesoporous Y-type zeolite containing titanium, which is prepared by the following steps:
40.0g of overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The skeleton silicon-aluminum ratio is 5.1, na 2 O content is 13.8wt%) is placed in a quartz reaction tube, high-purity nitrogen is introduced, after leak detection is carried out, the nitrogen purging rate is set to be 50ml/min (glass rotameter), the heating program of the tubular furnace reactor is set, the temperature is raised from the initial temperature of 20 ℃ to 550 ℃ through 53min, then the temperature is kept for 60min, the temperature is naturally lowered to 500 ℃ and kept constant, and high-purity nitrogen saturated by TiCl 4 and SiCl 4 gas is introduced, wherein the titanium tetrachloride consumption is 9.0g, the silicon tetrachloride consumption is 1.0g, and the contact time is 75min. Stopping introducing high-purity nitrogen saturated by TiCl 4 and SiCl 4 after the reaction is finished, continuing to purge the high-purity nitrogen for 120min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a 90 ℃ water bath, filtering until the filtrate is neutral, taking out a filter cake, and drying the filter cake in a 120 ℃ oven overnight. Finally, the gas phase ultrastable mesoporous Y-type zeolite containing titanium is obtained.
The Y-zeolite obtained in this example was characterized by the relevant tests, and the phase structure, texture properties, and elemental composition results are shown in table 1.
Comparative example 1
The comparative example provides a conventional gas-phase ultrastable Y-type zeolite prepared by reacting SiCl 4 as a dealumination reagent with NaY zeolite, and the conventional gas-phase ultrastable Y-type zeolite is prepared by the following steps:
80.0g of an overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The framework silicon-aluminum ratio is 5.1, na 2 O content is 13.8wt%) is placed in a quartz reaction tube, high-purity nitrogen is introduced, after leak detection is carried out, the nitrogen purging rate is set to be 50ml/min (glass rotameter), the heating program of the tubular furnace reactor is set, namely the temperature is raised from the initial temperature of 20 ℃ to 550 ℃ through 53min and then kept for 120min, the temperature is naturally lowered to 410 ℃ and then kept constant, and high-purity nitrogen saturated by SiCl 4 gas is introduced, wherein the silicon tetrachloride consumption is 12.0g, and the contact time is 120min. Stopping introducing high-purity nitrogen saturated by SiCl 4 gas after the reaction is finished, continuing to purge the high-purity nitrogen for 120min, stopping constant temperature, taking out a solid-phase product when the reactor is naturally cooled to be lower than 200 ℃, mixing the solid-phase product with deionized water, stirring the mixed slurry for 1h under the heating of a water bath at 90 ℃, carrying out suction filtration until filtrate is neutral, taking out a filter cake, and drying overnight in a 120 ℃ oven. Finally, the common gas-phase ultrastable Y-type zeolite is obtained and is marked as DY zeolite.
The DY zeolite obtained in this comparative example was subjected to the relevant test characterization, and the phase structure, texture properties, and elemental composition results are shown in Table 1.
Comparative example 2
The embodiment provides a method for preparing ultra-stable Y-type zeolite containing mesopores by a hydrothermal method, which comprises the following steps:
100.0g of overnight dried NaY zeolite (NaY zeolite having a relative crystallinity of 97% and a unit cell constant, supplied by catalyst works of Lanzhou petrochemical Co., ltd.) was weighed out The skeleton silicon-aluminum ratio is 5.1, the Na 2 O content is 13.8wt%, the ammonium chloride and the deionized water are mixed and pulped in a mass ratio of 1:1:10, the mixture is exchanged for 1h under the conditions that the temperature is 90 ℃ and the system pH=3.1, then the mixture is filtered until the filtrate is neutral, 100 percent of steam is introduced at 650 ℃ after the mixture is dried, and the hydrothermal treatment is carried out for 2h. Repeating the same steps again to obtain the ultra-stable Y-type zeolite which is named as USY zeolite
The USY-type zeolite obtained in this comparative example was subjected to the relevant test characterization, and the phase structure, texture properties, and elemental composition results are shown in Table 1.
Examples 7 to 9
Examples 7 to 9 illustrate the heavy oil catalytic cracking performance of the Y-type zeolite provided by the present invention and the Y-type zeolite of comparative examples 1 and 2.
The preparation method of the catalyst comprises the following steps:
Based on the dry matrix, 35wt% of zeolite, 15wt% of alumina sol and 50wt% of kaolin are fully mixed, and after spray forming, 100% steam is subjected to hydrothermal aging for 4 hours at 800 ℃, and the aged catalyst is stored in a dry and anhydrous atmosphere for standby.
Reaction evaluation:
The reaction was evaluated in a catalytic cracking fixed fluidized bed experimental apparatus (ACE reaction evaluation apparatus). The reaction raw materials are raw oil (density (20 ℃) of 0.93g/cm 3, residual carbon of 4.19wt%, saturated parts of 64.68wt%, aromatic parts of 28.44wt%, elemental analysis carbon content of 86.76wt%, elemental analysis hydrogen content of 11.63 wt%) of an industrial catalytic cracking device, oil inlet amount of 1.5g, feeding time of 75s, catalyst-oil ratio of 6 and cracking reaction temperature of 530 ℃. The cracked gas was analyzed on-line by gas chromatography. The carbon content on the catalyst adopts an online analysis method. The collected liquid product composition was analyzed for its composition using simulated distillation chromatography.
Example 7
The titanium-containing gas-phase ultrastable mesoporous Y-type zeolite obtained in example 3 was prepared into a catalyst, which was numbered CAT-1, according to the above catalyst preparation method. The reaction evaluation results are shown in Table 2.
Example 8
The gas-phase ultrastable Y-type zeolite obtained in comparative example 1 was prepared into a catalyst, numbered CAT-2, according to the catalyst preparation method described above. The reaction evaluation results are shown in Table 2.
Example 9
The titanium-containing hydrothermal ultrastable mesoporous Y-type zeolite obtained in comparative example 2 was prepared into a catalyst, numbered CAT-3, according to the catalyst preparation method described above. The reaction evaluation results are shown in Table 2.
Table 1 phase Structure, texture Properties and elemental composition of samples obtained in examples 1 to 6 and comparative examples 1 to 2
As can be seen from Table 1, the Y-type zeolite prepared by the invention has a considerable amount of mesoporous volume, the framework silicon-aluminum ratio is low, and a large amount of acid centers are reserved. Compared with the hydrothermal ultra-stable preparation process, the method has the advantages of simple process, time saving, production cost saving and environmental protection.
Table 2 ACE evaluation results for examples 7 to 9
a Conversion = (100-slurry%)/100
As can be seen from Table 2, the catalyst prepared from the Y-type zeolite obtained by the method of the present invention has high conversion rate, high light oil yield and low coke selectivity. And the catalyst prepared by the gas phase ultrastable product has high light oil yield compared with the catalyst prepared by the hydrothermal ultrastable product.
Fig. 1 shows XRD patterns of Y zeolite obtained in examples 1, 5 and 6 of the present invention, and as can be seen from fig. 1, the XRD patterns of three samples of example 1, example 5 and example 6 have the same characteristic line peak as that of NaY standard.
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 as defined in the appended claims.
Claims (11)
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