CN116063190B - Catalyst grading method for process of synthesizing diphenylamine from aniline - Google Patents
Catalyst grading method for process of synthesizing diphenylamine from aniline Download PDFInfo
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- CN116063190B CN116063190B CN202111278650.9A CN202111278650A CN116063190B CN 116063190 B CN116063190 B CN 116063190B CN 202111278650 A CN202111278650 A CN 202111278650A CN 116063190 B CN116063190 B CN 116063190B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000002194 synthesizing effect Effects 0.000 title abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 152
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 152
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 238000005470 impregnation Methods 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 15
- 239000006227 byproduct Substances 0.000 abstract description 10
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 18
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002824 redox indicator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst grading method for a process for synthesizing diphenylamine from aniline. Under the condensation condition, aniline raw materials sequentially pass through two catalyst beds of a fixed bed reactor, wherein the first catalyst bed is filled with a beta/Y composite molecular sieve catalyst, and the second catalyst bed is filled with a beta molecular sieve catalyst. The invention carries out grading on two acidic molecular sieve catalysts, which not only can obtain higher conversion rate, but also reduces the content of macromolecular byproducts in the product, thereby improving the selectivity of the target product.
Description
Technical Field
The invention relates to a catalyst grading method for a diphenylamine synthesis process, in particular to a grading method for two different molecular sieve catalysts.
Background
Diphenylamine is an important organic chemical raw material and has very wide application. The method is mainly used for synthesizing rubber as an anti-aging agent, an explosive stabilizer, a fuel and medical intermediate, azo dyes, a fruit preservative and the like in industry, and can also be used as an analysis reagent for identifying DNA, nitrate, nitrite, chlorate and magnesium as colorimetric determination and redox indicators. At present, most catalysts for synthesizing diphenylamine from aniline introduced in domestic and foreign patent technologies are solid acid catalysts, and patents such as US3118944, US4454348, US3944613, CN94107296.7 and the like disclose technologies for preparing the catalysts by adopting activated alumina, amorphous silica-alumina and molecular sieves.
The reaction of synthesizing diphenylamine from phenylamine is a typical acid catalytic reaction, and the acidity of the catalyst directly influences the reaction performance. In the middle 90 th century, new technology for continuously synthesizing diphenylamine from phenylamine and matched special molecular sieve catalyst are developed successfully, and its active component is H beta molecular sieve. The H beta molecular sieve is a high-silicon molecular sieve with twelve-membered ring pore canal structure, the silicon-aluminum ratio is generally 25-28, the high-silicon molecular sieve has acidity and pore canal structure suitable for synthesizing diphenylamine from aniline, the high-silicon molecular sieve has two independent pore canal structures, one pore canal has the pore diameter of 0.66nm multiplied by 0.67nm, the other is a curved channel system formed by intersecting two linear channels, and the pore diameter of the curved channel system is 0.56nm multiplied by 0.56nm. The pore diameter can just allow a single benzene ring or a molecule with a linear biphenyl structure to pass through, and can effectively limit the generation of branched aromatic species with larger molecular size or the outward diffusion of pore channels, such as anthracene condensed ring species, acridine, quinoline and the like, so that excellent diphenylamine selectivity can be obtained. In addition, the selectivity of the catalyst is also influenced by the acid amount of the catalyst, when the acid amount of the catalyst is high and the acid density is high, the generated target product is extremely easy to be captured again by an acid center, and further acid-catalyzed cyclization, isomerization, condensation and other reactions occur to generate byproducts, so that the selectivity of the target product is reduced. Thus, how to obtain both high activity and high selectivity is an important issue facing this technology.
Disclosure of Invention
In order to overcome the defects in the prior art, the first aspect of the invention provides a catalyst grading method for synthesizing diphenylamine from aniline. The catalyst grading method carries out grading on two acidic molecular sieve catalysts, so that the catalyst has higher aniline conversion rate, further condensation or cyclization of diphenylamine products can be effectively avoided, the content of macromolecular byproducts in the products is reduced, and the selectivity of target products is improved.
The invention provides a beta/Y composite molecular sieve catalyst and a grading method of the beta molecular sieve catalyst, which comprises the following contents: under the condensation condition, aniline raw materials sequentially pass through two catalyst beds of a fixed bed reactor, wherein the first catalyst bed is filled with a beta/Y composite molecular sieve catalyst, and the second catalyst bed is filled with a beta molecular sieve catalyst.
Further, the volume ratio of the beta/Y composite molecular sieve catalyst to the beta molecular sieve catalyst is generally 1:1-6, preferably 1:1.5-5.
Further, the condensation reaction conditions include: the reaction pressure is 1.0-6.0 MPa, preferably 1.5-3.0 MPa; the reaction temperature is 200-400 ℃, preferably 280-380 ℃; the liquid hourly space velocity is 0.1-0.5 h -1, preferably 0.1-0.3 h -1. Further, the reaction temperature t2 of the second bed is higher than the reaction temperature t1 of the first bed, preferably t2 is 2 to 45 ℃ higher than t1, more preferably t2 is 5 to 30 ℃ higher than t 1.
Further, the beta/Y composite molecular sieve catalyst comprises, based on the weight of the catalyst:
60% -75%, preferably 65% -72% of H beta molecular sieve;
5% -20%, preferably 8% -15% of an HY molecular sieve;
0.5% -12% of metal calculated by oxide, preferably 4.5% -10%;
10% -34.5% of aluminum oxide, preferably 10% -22.5%;
Wherein the molar ratio of silicon to aluminum of the H beta molecular sieve is 20-300, preferably 25-200; the molar ratio of silicon to aluminum of the HY molecular sieve is 1.0-4.0, preferably 1.5-3.0.
Further, the beta/Y composite molecular sieve catalyst is a bar-shaped or spherical particle, the cross section of the catalyst can be cylindrical, clover or a vast expanse of country grass shape when the catalyst is bar-shaped, and the diameter of the bar-shaped particle is 0.5-3.0 mm, preferably 1.0-2.0 mm; in the case of spherical particles, the diameter is 0.5 to 5.0mm, preferably 1.0 to 3.0mm. The specific surface area of the catalyst is 300-600 m 2/g, preferably 400-550 m 2/g; the specific pore volume is 0.25-0.50 mL/g, preferably 0.30-0.45 mL/g; the average pore diameter is 1.5 to 5nm, preferably 2.0 to 4.0nm.
Further, the metal is selected from at least one of Li, na, K, mg, ca, sr, la, ce, pr, zr, cu, preferably La and/or Ce.
Further, the catalyst may further contain a non-metal oxide such as one or more oxides of Si, P, B, C. The content of the nonmetallic oxide in the catalyst is generally 0.01% -5%. The addition of the non-metal oxide promoter may further improve the acid distribution or specific surface area of the catalyst.
In the present invention, the beta/Y composite molecular sieve catalyst may be prepared by conventional methods in the art. In the invention, the beta/Y composite molecular sieve catalyst is recommended to be prepared by the following method:
(1) And (3) carrying out metal modification on the HY molecular sieve by adopting an impregnation mode, and then drying and roasting.
(2) Fully kneading the H beta molecular sieve, the HY molecular sieve obtained in the step (1), an alumina precursor, an extrusion aid and a peptizing agent solution according to a certain proportion, forming, drying and roasting to obtain a catalyst precursor;
(3) And (3) carrying out metal modification on the catalyst precursor obtained in the step (2) by adopting an impregnation mode to obtain the finished catalyst.
Further, the operation of step (2) is well known to those skilled in the art. For example, the weight ratio of the H beta molecular sieve, the HY molecular sieve, the alumina, the extrusion aid and the peptizing agent solution is (60-75): (5-20): (15-40): (3-20): (5-80), preferably (65-72): (8-15): (20-30): (10-15): (20-50). In the material consumption, the H beta molecular sieve, the HY molecular sieve and the alumina precursor are all weight based on dry basis.
Further, the extrusion aid may be selected from sesbania powder. The peptizing agent may be selected from dilute nitric acid solution or citric acid. The mass concentration of the dilute nitric acid solution is 3% -15%.
Further, the drying conditions in the steps (1) and (2) are as follows: the drying temperature is 60-150 ℃, preferably 80-120 ℃, and the drying time is 8-24 hours, preferably 10-20 hours. Preferably naturally drying in the shade for 10-48 h before drying. The roasting conditions are as follows: the roasting temperature is 300-800 ℃, preferably 400-700 ℃, and the roasting time is 2-24 hours, preferably 4-8 hours.
Further, the metal in step (1) and (3) is at least one selected from Li, na, K, mg, ca, sr, la, ce, pr, zr, cu, preferably La and/or Ce. The metal precursor used is a nitrate or chloride of the metal. After impregnation, the materials are dried and roasted. Impregnation, drying and calcination processes are well known to those skilled in the art. The addition amount of the metal in terms of elements is 4.5% -12%, preferably 5% -10% of the weight of the finished catalyst.
Further, the beta molecular sieve catalyst comprises, by weight:
50% -85%, preferably 65% -80% of the H beta molecular sieve;
0.1% -5%, preferably 0.5% -4.6% of metal in terms of oxide;
10% -49.9% of aluminum oxide, preferably 15% -34.5%;
wherein the molar ratio of silicon to aluminum of the H beta molecular sieve is 20-300, preferably 30-200.
Further, the beta molecular sieve catalyst can be bar-shaped or spherical particles, and when the beta molecular sieve catalyst is bar-shaped, the cross section of the beta molecular sieve catalyst can be cylindrical, clover or a vast expanse of country grass-shaped, and the diameter of the beta molecular sieve catalyst is 0.5-3.0 mm, preferably 1.0-2.0 mm; in the case of a spherical shape, the diameter is 0.5 to 5.0mm, preferably 1.0 to 3.0mm. The specific surface area of the catalyst is 300-600 m 2/g, preferably 400-550 m 2/g; the specific pore volume is 0.25-0.50 mL/g, preferably 0.30-0.45 mL/g; the average pore diameter is 1.5 to 5nm, preferably 2.0 to 4.0nm.
Further, the metal in the beta molecular sieve catalyst is selected from at least one of Li, na, K, mg, ca, sr, la, ce, pr, zr, cu, preferably Na or Mg.
Further, the beta molecular sieve catalyst may further comprise a non-metal oxide, such as one or more oxides of Si, P, B, C. The content of the nonmetallic oxide in the catalyst is generally 0.01% -5%. The addition of the non-metal oxide promoter may further improve the acid distribution or specific surface area of the catalyst.
Further, the alumina is preferably alumina obtained by pre-roasting pseudo-boehmite at 800-1200 ℃. The calcined alumina crystal form can be delta type, theta type or alpha type single crystal type structure, or can be a composite structure of two crystal forms.
Further, the beta molecular sieve catalyst may be prepared by the following method:
a) Pre-roasting pseudo-boehmite at 800-1200 ℃ to obtain single-crystal or composite crystal alumina;
b) Fully kneading an H beta molecular sieve, an alumina precursor, an extrusion assisting agent and a peptizing agent solution according to a certain proportion, forming, drying and roasting to prepare a catalyst precursor;
c) And c) carrying out metal modification on the catalyst precursor obtained in the step b) by adopting an impregnation mode to obtain the finished catalyst.
Further, the pre-calcination temperature of the pseudo-boehmite in the step a) is 800-1200 ℃, preferably 850-1150 ℃, and the calcination time is 1-10 hours, preferably 2-6 hours. The calcined alumina crystal form can be a delta type, theta type or alpha type single crystal structure, or can be a composite structure of two crystal forms.
Further, the operation of step b) is well known to those skilled in the art. For example, the ratio of the H beta molecular sieve, the alumina obtained in the step a), the extrusion aid and the peptizer is 100: (15-50): (3-20): (5-80), preferably 100: (20-35): (10-15): (20-50). In the material dosage, the H beta molecular sieve and the alumina precursor are calculated by the weight of a dry basis. The extrusion aid may be selected from sesbania powder. The peptizing agent may be selected from dilute nitric acid solution or citric acid. The mass concentration of the dilute nitric acid solution is 3% -15%.
Further, the drying conditions in the step (2) are as follows: the drying temperature is 60-150 ℃, preferably 80-120 ℃, and the drying time is 8-24 hours, preferably 10-20 hours. Preferably naturally drying in the shade for 10-48 h before drying. The roasting conditions are as follows: the roasting temperature is 300-800 ℃, preferably 400-700 ℃, and the roasting time is 2-24 hours, preferably 4-8 hours.
Further, the metal of step c) is selected from at least one of Li, na, K, mg, ca, sr, la, ce, pr, zr, cu, preferably Na or Mg. The metal precursor used is a nitrate or chloride of the metal. After impregnation, the materials are dried and roasted. Impregnation, drying and calcination processes are well known to those skilled in the art. The addition amount of the metal in terms of elements is 0.1% -5.0% of the weight of the finished catalyst, and preferably 0.3% -4.6%.
The applicant has studied the ammonification reaction and its catalyst to reach the following conclusion: the reaction of synthesizing diphenylamine from phenylamine is a typical acid catalytic reaction, and the acidity of the catalyst directly influences the reaction performance. The H beta molecular sieve has a silicon-aluminum ratio of 25-28, has an acidity and a pore canal structure suitable for synthesizing diphenylamine from aniline, and has two independent pore canal structures, wherein the pore diameter of one pore canal is 0.66nm multiplied by 0.67nm, and the other pore canal is a curved channel system formed by intersecting two linear channels, and the pore diameter of the curved channel system is 0.56nm multiplied by 0.56nm. The pore diameter can just allow a single benzene ring or a molecule with a linear biphenyl structure to pass through, and can effectively limit the generation of branched aromatic species with larger molecular size or the outward diffusion of pore channels, such as anthracene condensed ring species, acridine, quinoline and the like, so that excellent diphenylamine selectivity can be obtained. In the prior art, the selectivity of the reaction for synthesizing the diphenylamine by catalyzing the phenylamine by using the H beta molecular sieve catalyst is higher, but the conversion rate of the phenylamine is generally only 20% -25%, and the activity of the catalyst is lower. And a large amount of unreacted aniline needs to be separated and then is reacted again, and the energy consumption for separating the product is high. In order to improve the conversion rate of aniline, research in recent years mainly focuses on modulating or modifying the acidity and pore channels of beta molecular sieves. However, the conversion rate and selectivity of the existing catalyst cannot be considered. The inventors found that: the HY molecular sieve is the same as the H beta molecular sieve, has a twelve-membered ring pore channel structure, has the pore diameter of 0.74nm multiplied by 0.74nm, is close to the H beta molecular sieve, and can obtain higher product selectivity. Importantly, the HY molecular sieve has low silicon-aluminum ratio, usually below 4.0, and a large number of acid centers, can provide rich active sites, and achieves higher aniline conversion rate.
However, the present inventors have studied to find that: if the HY molecular sieve is simply introduced, although the equilibrium conversion rate of aniline can be improved, the problems of selectivity reduction and stability deterioration can be caused, and the problems are the root cause that the catalyst cannot be used for synthesizing diphenylamine from aniline. In the application, after the HY molecular sieve is introduced, the dosage of the modified metal needs to be increased in consideration of the acidity and the increase of the acid density; on the one hand, the strong acid center can be covered, and more importantly, the pore canal of the introduced HY molecular sieve can be modified appropriately. The modified metal is preferably La and/or Ce, and the large-size oxide can be obtained after roasting, and is attached to the inner surface and the orifice position of the pore canal of the HY molecular sieve, so that the bending degree of the pore canal of the HY molecular sieve is increased, the orifice diameter of the HY molecular sieve is reduced, and the large-molecular byproducts are generated in the catalyst pore canal without enough space and are diffused out from the orifice, so that the generation of the large-molecular byproducts is reduced. Therefore, the method can reduce the yield of macromolecular byproducts and keep the selectivity of the diphenylamine to be basically equivalent to or slightly increased as before while introducing the HY molecular sieve to modulate the acid amount and the acid density of the catalyst. Modification of the molecular sieve pore channels and openings also reduces the propensity of aniline molecules or fragments to cyclize, coke, and form carbon deposits within the pore channels. Namely, the stability of the catalyst is improved, and the service life of the catalyst is prolonged. In addition, the selectivity of the catalyst is also influenced by the acid amount of the catalyst, when the acid amount of the catalyst is high and the acid density is high, the generated target product is extremely easy to be captured again by an acid center, and further acid-catalyzed cyclization, isomerization, condensation and other reactions occur to generate byproducts, so that the selectivity of the target product is reduced. The beta/Y composite molecular sieve catalyst and the beta molecular sieve catalyst are graded for use, so that the aniline raw material firstly passes through the beta/Y composite molecular sieve catalyst bed to obtain higher aniline conversion rate, and then passes through the beta molecular sieve catalyst bed to limit the product to further undergo side reaction, thereby effectively improving the product selectivity.
Compared with the prior art, the method has the following beneficial effects:
1. The beta/Y composite molecular sieve catalyst used in the process of the invention has higher conversion and substantially equivalent selectivity compared to beta molecular sieve catalysts. The raw material aniline and the composite molecular sieve catalyst of the first bed layer are in contact reaction, and can be subjected to conversion reaction at relatively low temperature, so that the generation of macromolecule byproducts such as acridine, quinoline and the like is reduced on the premise of maintaining the conversion rate not to be reduced or even being improved to some extent. While the effluent from the first bed, when passing through the beta/molecular sieve catalyst bed of the second bed, may continue to be converted to diphenylamine at a relatively high temperature, resulting in higher conversion rates while producing less macromolecular byproducts. Thus, the catalyst grading scheme of the present invention has higher conversion and better selectivity.
2. The beta/Y composite molecular sieve catalyst used in the method has higher acidity and more proper acid distribution; and after the metal modification is introduced, the catalyst has proper pore size, and has higher activity and basically equivalent product selectivity when being used for synthesizing diphenylamine from aniline.
3. In the preparation process of the catalyst, the precursor pseudo-boehmite of the binder alumina is pre-baked at a temperature far higher than the conventional conditions, so that the precursor pseudo-boehmite is pre-crystallized into a delta type, theta type or alpha type single crystal type or two crystal type composite structure, and the total acid amount of the alumina can be greatly reduced, and especially the acid density is greatly reduced. The alumina after pre-roasting and crystal transformation is kneaded with a molecular sieve to form and load modified metal to prepare the finished beta/molecular sieve catalyst, the total acid amount of the catalyst is low, side reactions are reduced, the selectivity is improved, and the catalyst has good stability and long one-way operation period.
4. The catalyst grading method has high product selectivity and less byproduct heavy components, can effectively reduce the energy consumption of a separation section and reduce the solid waste discharge, thereby saving the production cost for enterprises.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention in detail, but the present invention is not limited to the following examples.
In the material consumption, the H beta molecular sieve, the HY molecular sieve and the alumina precursor are all weight based on dry basis.
Example 1
La is loaded on an HY molecular sieve with a silicon-aluminum ratio of 1.6 in an impregnation mode, dried for 4 hours at 110 ℃, and baked for 4 hours at 550 ℃. Uniformly mixing an H beta molecular sieve with a silicon-aluminum ratio of 52, a modified HY molecular sieve, pseudo-boehmite, sesbania powder and a dilute nitric acid solution (10 wt%) according to a certain mass ratio, extruding and molding, drying in the shade for 24 hours, drying in an oven at 110 ℃ for 16 hours, and roasting at 540 ℃ for 4 hours. La is loaded in an impregnation mode, and the catalyst is dried for 3 hours at 120 ℃ and baked for 3 hours at 540 ℃ to obtain the finished catalyst. The catalyst comprises the following components: 66.1% of H beta molecular sieve, 7.2% of HY molecular sieve, 8.5% of lanthanum oxide and 18.2% of aluminum oxide.
The pseudo-boehmite is baked for 6 hours at 1050 ℃ and then is transformed into theta-alumina. Mixing H beta molecular sieve with silicon-aluminum ratio of 75, alumina, sesbania powder and dilute nitric acid solution (10 wt%) uniformly according to a certain mass ratio, extruding and forming, drying in the shade for 24 hr, drying in oven at 110 deg.C for 16 hr, and roasting at 540 deg.C for 4 hr. Na is loaded in an impregnation mode, and the finished catalyst is obtained after the drying at 120 ℃ for 3 hours and the roasting at 540 ℃ for 3 hours. The catalyst comprises the following components: the H beta molecular sieve content is 78.1%, the sodium oxide content is 2.4%, and the alumina content is 19.5%.
The beta/Y composite molecular sieve catalyst and the beta molecular sieve catalyst are filled according to the volume ratio of 1:4, and the aniline material firstly contacts the beta/Y composite molecular sieve catalyst bed layer and then contacts the beta molecular sieve catalyst bed layer. This scheme is designated a.
Comparative example 1
Referring to the preparation scheme of the beta/Y composite molecular sieve catalyst in example 1, the catalyst bed is fully filled with the beta/Y composite molecular sieve catalyst. This scheme is designated B1.
Comparative example 2
Referring to the preparation scheme of the beta molecular sieve catalyst in example 1, the catalyst bed was fully loaded with beta molecular sieve catalyst. This scheme is designated B2.
Comparative example 3
Referring to the beta/Y composite molecular sieve catalyst and the preparation scheme of the beta molecular sieve catalyst in the embodiment 1, the beta/Y composite molecular sieve catalyst and the beta molecular sieve catalyst are filled according to the volume ratio of 1:4, and the aniline material is firstly contacted with the beta molecular sieve catalyst bed layer and then contacted with the beta/Y composite molecular sieve catalyst bed layer. This scheme is designated B3.
Example 2
Ce is loaded on an HY molecular sieve with a silicon-aluminum ratio of 2.0 by adopting a dipping mode, dried for 4 hours at 110 ℃, and baked for 4 hours at 550 ℃. Uniformly mixing an H beta molecular sieve with a silicon-aluminum ratio of 45, a modified HY molecular sieve, pseudo-boehmite, sesbania powder and a dilute nitric acid solution (10 wt%) according to a certain mass ratio, extruding and molding, drying in the shade for 24 hours, drying in an oven at 120 ℃ for 24 hours, and roasting at 560 ℃ for 4 hours. Ce is loaded in an impregnation mode, and the catalyst is dried for 3 hours at 120 ℃ and baked for 3 hours at 540 ℃ to obtain the finished catalyst. The catalyst comprises the following components: 61.2% of H beta molecular sieve, 11.2% of HY molecular sieve, 9% of cerium oxide and 18.6% of aluminum oxide.
The pseudo-boehmite is baked for 5 hours at 950 ℃ and is transformed into theta+delta alumina. Mixing H beta molecular sieve with silicon-aluminum ratio of 50, alumina, sesbania powder and dilute nitric acid solution (10 wt%) uniformly according to a certain mass ratio, extruding and forming, drying in the shade for 24 hr, drying in oven at 120 deg.C for 18 hr, and roasting at 540 deg.C for 4 hr. Mg is loaded in an impregnation mode, and the catalyst is dried for 3 hours at 110 ℃ and baked for 3 hours at 550 ℃ to obtain the finished catalyst. The catalyst comprises the following components: the H beta molecular sieve content is 78.2%, the magnesia content is 1.8% and the alumina content is 20%.
The beta/Y composite molecular sieve catalyst and the beta molecular sieve catalyst are filled according to the weight ratio of 1:3, and the aniline material firstly contacts the beta/Y composite molecular sieve catalyst bed layer and then contacts the beta molecular sieve catalyst bed layer. This scheme is designated C.
Example 3
K is loaded on an HY molecular sieve with a silicon-aluminum ratio of 1.6 in an impregnation mode, dried for 4 hours at 110 ℃, and baked for 4 hours at 550 ℃. Uniformly mixing an H beta molecular sieve with a silicon-aluminum ratio of 52, a modified HY molecular sieve, pseudo-boehmite, sesbania powder and a dilute nitric acid solution (10 wt%) according to a certain mass ratio, extruding and molding, drying in the shade for 24 hours, drying in an oven at 110 ℃ for 16 hours, and roasting at 540 ℃ for 4 hours. K is loaded by adopting an impregnation mode, and the finished catalyst is obtained after drying for 3 hours at 120 ℃ and roasting for 3 hours at 540 ℃. The catalyst comprises the following components: 66.1% of H beta molecular sieve, 7.2% of HY molecular sieve, 8.5% of potassium oxide and 18.2% of alumina.
The pseudo-boehmite is baked for 5 hours at 950 ℃ and is transformed into theta+delta alumina. Mixing H beta molecular sieve with silicon-aluminum ratio of 50, alumina, sesbania powder and dilute nitric acid solution (10 wt%) uniformly according to a certain mass ratio, extruding and forming, drying in the shade for 24 hr, drying in oven at 120 deg.C for 18 hr, and roasting at 540 deg.C for 4 hr. K is loaded by adopting an impregnation mode, and the finished catalyst is obtained after drying for 3 hours at 110 ℃ and roasting for 3 hours at 550 ℃. The catalyst comprises the following components: the H beta molecular sieve content is 78%, the potassium oxide content is 2.2%, and the alumina content is 19.8%.
The beta/Y composite molecular sieve catalyst and the beta molecular sieve catalyst are filled according to the weight ratio of 1:4, and the aniline material firstly contacts the beta/Y composite molecular sieve catalyst bed layer and then contacts the beta molecular sieve catalyst bed layer. This scheme is designated D.
Example 4
The catalysts prepared in the examples and the comparative examples are adopted to carry out an evaluation experiment of synthesizing diphenylamine from aniline in a miniature evaluation device, wherein aniline is used as a raw material, the reaction temperature is 300 ℃, the reaction pressure is 4.0MPa, and the volume space velocity of the aniline is 0.2h -1.
TABLE 1
Examples 5 to 8
The beta/Y composite molecular sieve catalyst prepared in example 2 was selected from beta molecular sieve catalysts, with the first bed packed with beta/Y composite molecular sieve catalyst and the second bed packed with H beta molecular sieve catalyst. Under different technological conditions, catalyzing aniline to synthesize diphenylamine. The process conditions and test results are shown in Table 2.
TABLE 2
Claims (18)
1. The grading method of the diphenylamine synthesis process comprises the following steps: under the condensation condition, aniline raw materials sequentially pass through two catalyst beds of a fixed bed reactor, wherein the first catalyst bed is filled with a beta/Y composite molecular sieve catalyst, and the second catalyst bed is filled with a beta molecular sieve catalyst;
The beta/Y composite molecular sieve catalyst comprises the following components by weight of the catalyst:
60% -75% of H beta molecular sieve;
5% -20% of HY molecular sieve;
4.5% -12% of metal in terms of oxide;
10% -34.5% of aluminum oxide;
Wherein the molar ratio of silicon to aluminum of the H beta molecular sieve is 20-300, and the molar ratio of silicon to aluminum of the HY molecular sieve is 1.0-4.0; at least one metal selected from Li, na, K, mg, ca, sr, la, ce, pr, zr, cu;
the preparation method of the beta/Y composite molecular sieve catalyst comprises the following steps:
(1) Carrying out metal modification on the HY molecular sieve by adopting an impregnation mode, and then drying and roasting;
(2) Fully kneading an H beta molecular sieve, an HY molecular sieve, alumina, an extrusion aid and a peptizing agent solution according to a certain proportion, forming, drying and roasting to prepare a catalyst precursor;
(3) And (3) carrying out metal modification on the catalyst precursor obtained in the step (2) by adopting an impregnation mode to obtain the finished catalyst.
2. The grading method according to claim 1, wherein the volume ratio of the beta/Y composite molecular sieve catalyst to the beta molecular sieve catalyst is 1:1-6.
3. The grading process according to claim 1, wherein the condensation reaction conditions comprise: the reaction pressure is 1.0-6.0 MPa, the reaction temperature is 200-400 ℃, and the liquid hourly space velocity is 0.1-0.5 h -1.
4. A grading process according to claim 3, wherein the condensation reaction conditions comprise: the reaction pressure is 1.5-3.0 MPa, the reaction temperature is 280-380 ℃, and the liquid hourly space velocity is 0.1-0.3 h -1.
5. The grading process according to claim 4, wherein the reaction temperature t2 of the second bed is higher than the reaction temperature t1 of the first bed.
6. The grading method according to claim 5, wherein t2 is 2 to 45℃higher than t 1.
7. The grading process according to claim 1, wherein the beta/Y composite molecular sieve catalyst comprises, based on the weight of the catalyst:
65% -72% of H beta molecular sieve;
8% -15% of HY molecular sieve;
5% -10% of metal in terms of oxide;
10% -22.5% of aluminum oxide;
Wherein the molar ratio of silicon to aluminum of the H beta molecular sieve is 25-200; the molar ratio of silicon to aluminum of the HY molecular sieve is 1.5-3.0.
8. The grading process according to claim 1, wherein the beta/Y composite molecular sieve catalyst is in the form of bar or sphere particles.
9. The grading method according to claim 8, wherein the diameter of the bar-shaped particles is 0.5 to 3.0mm, and the diameter of the spherical particles is 0.5 to 5.0mm.
10. The grading method according to claim 1, wherein the specific surface area of the beta/Y composite molecular sieve catalyst is 300-600 m 2/g, the specific pore volume is 0.25-0.50 mL/g, and the average pore diameter is 1.5-5 nm.
11. The grading method according to claim 1, characterized in that the metal is selected from La and/or Ce.
12. The grading method according to claim 1, wherein in the step (2), the weight ratio of the H beta molecular sieve to the HY molecular sieve to the alumina to the extrusion aid to the peptizing agent solution is (60-75): (5-20): (15-40): (3-20): (5-80).
13. The grading method according to claim 1, wherein the metal of step (1) and step (3) is at least one selected from Li, na, K, mg, ca, sr, la, ce, pr, zr, cu.
14. The grading process according to claim 1, wherein the beta molecular sieve catalyst comprises, on a weight basis: 50-85% of H beta molecular sieve, 0.1-5% of metal in terms of oxide, and 10-49.9% of alumina; the molar ratio of silicon to aluminum of the H beta molecular sieve is 20-300.
15. The grading process according to claim 14, wherein the beta molecular sieve catalyst comprises, on a weight basis: 65% -80% of H beta molecular sieve, 0.3% -4.6% of metal in terms of oxide, and 15% -34.5% of alumina; the molar ratio of silicon to aluminum of the H beta molecular sieve is 30-200.
16. The grading process according to claim 15, wherein the metal contained in the beta molecular sieve catalyst is at least one selected from Li, na, K, mg, ca, sr, la, ce, pr, zr, cu.
17. The grading process according to claim 16, wherein the metal contained in the beta molecular sieve catalyst is selected from Na or Mg.
18. The grading method according to claim 14, wherein the alumina in the beta molecular sieve catalyst is alumina obtained by pre-roasting pseudo-boehmite at 800-1200 ℃, and the roasted alumina crystal form is delta type, theta type or alpha type or a composite structure of two crystal forms.
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