CN117658758A - Production method of long-chain alkyl aromatic hydrocarbon - Google Patents
Production method of long-chain alkyl aromatic hydrocarbon Download PDFInfo
- Publication number
- CN117658758A CN117658758A CN202211059250.3A CN202211059250A CN117658758A CN 117658758 A CN117658758 A CN 117658758A CN 202211059250 A CN202211059250 A CN 202211059250A CN 117658758 A CN117658758 A CN 117658758A
- Authority
- CN
- China
- Prior art keywords
- solid acid
- acid catalyst
- long
- aromatic hydrocarbon
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 alkyl aromatic hydrocarbon Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 103
- 239000011973 solid acid Substances 0.000 claims abstract description 73
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000011069 regeneration method Methods 0.000 claims abstract description 52
- 230000008929 regeneration Effects 0.000 claims abstract description 40
- 150000001336 alkenes Chemical class 0.000 claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 25
- 239000010457 zeolite Substances 0.000 claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 230000029936 alkylation Effects 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 9
- 150000004996 alkyl benzenes Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VQOXUMQBYILCKR-UHFFFAOYSA-N tridecaene Natural products CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/70—Catalytic processes with acids
-
- 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- C07C2529/12—Noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The production method of the long-chain alkyl aromatic hydrocarbon is characterized by comprising an alkylation reaction process of long-chain olefin and aromatic hydrocarbon and a regeneration process of a solid acid catalyst, wherein the solid acid catalyst is Y-type zeolite loaded with a metal component with hydrogenolysis performance, the unit cell of the Y-type zeolite is 2.448-2.457 nm, the ratio of the mesoporous volume of the Y-type zeolite to the total pore volume is 0.15-0.29, and the metal component with hydrogenolysis performance accounts for 0.15-5wt% of the solid acid catalyst; the regeneration process of the solid acid catalyst is to heat the solid acid catalyst to 300-460 ℃ in a hydrogen atmosphere at a hydrogen heating rate of 1-15 ℃/min and treat the solid acid catalyst for at least 5 hours under the conditions of the temperature and 1.5-3MPa and a hydrogen flow of 150-500 mL/min/g.
Description
Technical Field
The invention relates to a method for producing long-chain alkyl aromatic hydrocarbon, in particular to a method for producing long-chain alkyl aromatic hydrocarbon by using solid acid as a catalyst.
Background
The linear alkylbenzene obtained by alkylation reaction of benzene and long-chain olefin is an important chemical intermediate for synthesizing washing products, and the intermediate can obtain the anionic surfactant-alkylbenzene sulfonate with excellent performance after sulfonation, neutralization and other reactions. The alkylation reaction of benzene and long-chain olefin lays the foundation of the industry of synthesizing washing products.
At present, 83% of the global linear alkylbenzene yield adopts an HF process and 9% adopts AlCl 3 The process, 8% use the Detal process.
HF process and AlCl 3 The process has the defects of high environmental pollution, serious equipment corrosion, difficult product separation and high cost investment. The Detal process is a solid acid process, which has been developed by UOP and CEPSA Petroleum in Spain in the United states, and has been industrialized in the middle of the nineties of the last century. The Detal process uses a fluorine-containing amorphous silicon-aluminum catalyst, and has the problems of fluorine loss, discontinuous alkylation reaction and catalyst regeneration process, high operation cost, frequent regeneration and the like in the operation process, so that the popularization and development of the catalyst are limited to a certain extent, and the environment-friendly solid acid alkylation technology is a development trend.
In the research of synthesizing linear alkylbenzene by using solid acid to catalyze benzene and long-chain olefin, molecular sieve and heteropolyacid solid acid catalyst are adopted. However, the problems of easy deactivation and short single cycle life of the catalyst are not solved effectively.
The current research is focused on catalytic materials or optimizing the process flow to improve the single-cycle operation time, and the problems of poor catalytic material effect, frequent process flow operation, high cost and the like exist. For example, CN1043524C discloses a process for benzene alkylation with fluorinated silica alumina and linear mono-olefins under alkylation conditions, benzene and C 6 To C 20 The linear mono-olefins are alkylated with benzene by contacting the benzene with a catalyst comprising a fluorinated silica alumina having a weight ratio of silica to alumina of from 1:1 to 9:1 and a fluoride content of from 1 to 6wt%, the process having 98% conversion of olefins, a selectivity to mono-alkylbenzene produced of 85% or better and a selectivity to mono-alkylbenzene of at least 90% of linearity with respect to monoalkylbenzene produced. The conversion rate of the method to olefin is still low, and the problem of environmental pollution caused by fluoride ion loss exists.
CN101535221B discloses a process for the preparation of alkylbenzenes with low benzene to olefin ratio and low heavies formation over solid acid catalysts. The process uses small crystal, acidic FAU molecular sieves as catalysts under alkylation conditions.
CN111514924a discloses a catalytic synthesis method of long-chain alkyl aromatic hydrocarbon, which comprises: firstly, inputting raw aromatic hydrocarbon into a fixed bed alkylation reactor, and filling the reactor; then the raw material arene and the raw material C 6 ～C 24 Inputting long-chain olefin and an additive long-chain alkyl aromatic hydrocarbon solvent or a mixture of long-chain alkane solvents into a fixed bed reactor, contacting with SBA-15 type mesoporous molecular sieve alkylation solid acid catalyst, and carrying out alkylation reaction of aromatic hydrocarbon and long-chain olefin to generate a product long-chain alkyl aromatic hydrocarbon; one portion of the alkylation reactor effluent is used as recycle stream to the reactor and the other portion is used as effluent stream to a distillation separation system to separate excess feedstock and product.
US5648579a discloses a process for alkylation of benzene with 1-dodecene using a pulse feed. In the method, benzene is always fed, and olefin is stopped at intervals, so that pulse feeding is realized, the molar ratio of benzene to olefin is 8-20, the carbon number of straight-chain olefin is 10-14, and the interval time of pulse feeding is 10-60 minutes.
Disclosure of Invention
The inventor finds that the solid acid catalyst prepared by loading the metal with hydrogenolysis activity on the solid acid with specific physicochemical characteristics has the activity of efficiently catalyzing alkylation reaction of benzene and long-chain olefin, and when the catalyst is deactivated, the catalyst contacts hydrogen under a certain condition to carry out regeneration reaction, so that the catalyst activity is recovered, and the catalyst can be ensured to maintain good selectivity and service life after regeneration for a plurality of times, thereby realizing long-period stable operation of an alkylation device. Based on this, the present invention is formed.
It is therefore an object of the present invention to provide a process for the production of long-chain alkylaromatic hydrocarbons which, unlike the prior art, allows both an increase in the single cycle run time of the alkylation reaction and a guarantee of long-cycle stable operation of the alkylation unit with complete regeneration of the solid acid catalyst.
In order to achieve the aim, the production method of the long-chain alkyl aromatic hydrocarbon is characterized by comprising an alkylation reaction process of long-chain olefin and aromatic hydrocarbon and a regeneration process of a solid acid catalyst, wherein in the alkylation reaction process of the long-chain olefin and the aromatic hydrocarbon, the alkylation reaction condition is that the temperature is 90-180 ℃, the pressure is 2.0-4.5 MPa, and the raw material mass airspeed is 1-30; the solid acid catalyst is Y-type zeolite loaded with metal components with hydrogenolysis performance, the unit cell of the Y-type zeolite is 2.448-2.457 nm, the ratio of the mesoporous volume to the total pore volume is 0.15-0.29, and the metal components with hydrogenolysis performance account for 0.2-2 wt% of the solid acid catalyst, preferably 0.4-1 wt%; the regeneration process of the catalyst is to heat the solid acid catalyst to 300-460 ℃ in a hydrogen atmosphere at a hydrogen heating rate of 1-15 ℃/min and treat the solid acid catalyst for at least 5 hours under the conditions of the temperature and 1.5-3.0MPa and a hydrogen flow of 150-500 mL/min/g.
In the invention, the aromatic hydrocarbon is one or more of monocyclic or polycyclic aromatic hydrocarbon, such as benzene, naphthalene, toluene, xylene, diethylbenzene, trimethylbenzene, triethylbenzene, tetramethylbenzene, isomers thereof and the like; preferably, the aromatic hydrocarbon is a monocyclic or bicyclic aromatic hydrocarbon. The total carbon number of the aromatic hydrocarbon is 6-18; preferably, the total carbon number of the aromatic hydrocarbon is 6-11; preferably, the aromatic hydrocarbon has a side chain number of 0 to 8, and preferably has a side chain number of 0 to 4. The most preferred aromatic hydrocarbon in the present invention is benzene.
In the present invention, the long-chain olefin is C 10 ～C 14 One or more of the long-chain olefins of (a). Such as long chain olefins: decene, undecene, dodecene, tridecene, tetradecene and isomers thereof.
In the invention, the solid acid catalyst comprises the Y-type zeolite and an inorganic oxide matrix, wherein the content of the Y-type zeolite is 40-95 wt% based on the solid acid catalyst.
The inventor researches and discovers that the deactivation of the alkylation reaction of the aromatic hydrocarbon and the long-chain olefin is caused by the fact that the heavy alkyl aromatic hydrocarbon generated in the reaction process blocks the pore canal of the catalyst, and the reaction can be catalyzed by the B acid or the L acid, so that the integrity of the crystal structure of the catalyst can be ensured by properly controlling the unit cell of the catalyst, and the reaction has enough active center of the B acid. Thus, the Y-type zeolite of the present invention has a unit cell of 2.448 to 2.457nm, preferably a unit cell of 2.452 to 2.455nm.
The inventor further researches and discovers that since the heavy alkyl aromatic hydrocarbon is a key for causing the deactivation of the catalyst, the mesoporous with a specific proportion can promote the timely diffusion of macromolecules such as the heavy alkyl aromatic hydrocarbon from the pore canal and delay the coking of the catalyst. The ratio of the mesoporous volume to the total pore volume is 0.15-0.29, preferably the ratio of the mesoporous volume to the total pore volume is 0.18-0.26. The mesoporous volume and total pore volume described in the present invention can be determined by the static low temperature nitrogen adsorption capacity method (BET). BET measurements are well known to those skilled in the art and can be performed, for example, using an ASAP2420 adsorber from America Micyoco, inc., as follows: firstly, drying a sample in an oven at 110 ℃ for 2 hours to remove surface water, then weighing a certain amount of sample, putting the sample into a degassing unit, vacuumizing to a vacuum degree of less than 1.33Pa, treating the sample at 90 ℃ for 1 hour, and then heating the sample to 330 ℃ for 9-10 hours; and (3) carrying out nitrogen adsorption and desorption test on the sample under the condition of liquid nitrogen cooling to obtain an adsorption-desorption curve, and calculating the specific surface area and the pore volume through a BET formula.
The Y-type zeolite is loaded with a proper amount of metal with hydrogenolysis performance, has a stronger synergistic catalytic effect with the B acid site, and has better alkylation activity and selectivity under the reaction condition of the invention. The metal with hydrogenolysis performance is selected from one or more of VIB, VIIB and VIII metals. Wherein the VIII metal is selected from one or more of Pt, pd and Ru, and the preferable one is Pt, and the Pt can not only generate synergistic action with B acid, but also can be used as a source of partial L acid center to improve the service life of the catalyst. The metal with hydrogenolysis performance accounts for 0.15 to 5wt% of the solid acid catalyst, preferably 0.2 to 2wt%, and more preferably 0.4 to 1wt%. The solid acid catalyst is prepared by impregnating Y-type zeolite with impregnating solution containing precursor of metal with hydrogenolysis performance, drying, roasting and reducing, and the precursor of Pt can be selected from one or more of chloroplatinic acid, ammonia chloroplatinate, potassium chloroplatinate, platinum tetrachloride or platinum tetrammine nitrate. The noble metal in the solid acid catalyst remains metallic as the alkylation reaction proceeds.
The inorganic oxide matrix is selected from one or more of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide.
In the invention, the regeneration process of the solid acid catalyst is carried out when the conversion rate of the long-chain olefin is less than 99% in the alkylation reaction process of the long-chain olefin and the aromatic hydrocarbon.
The regeneration process of the catalyst is to heat the solid acid catalyst to 300-460 ℃ in a hydrogen atmosphere at a hydrogen heating rate of 1-15 ℃/min and treat the solid acid catalyst for at least 5 hours under the conditions of the temperature and 1.5-3.0MPa and a hydrogen flow of 150-500 mL/min/g. Preferably, the condition of the regeneration process is that the temperature is raised to 340-420 ℃ at the hydrogen temperature rising rate of 1-10 ℃/min and the regeneration process is carried out for at least 5 hours under the conditions that the temperature is 2.0-2.8MPa and the hydrogen flow is 150-400 mL/min/g. In one embodiment of the invention, the deactivated solid acid catalyst is heated to 340-360 ℃ in a hydrogen atmosphere at a hydrogen heating rate of 2-8 ℃/min and treated for 6 hours under the conditions of 2.0-2.6MPa and a hydrogen flow rate of 200-400 mL/min/g.
According to the production method of the long-chain alkyl aromatic hydrocarbon, provided by the invention, aiming at a long-chain alkyl aromatic hydrocarbon reaction system, the solid acid catalyst is optimized from unit cells, mesoporous proportion, metal with hydrogenolysis performance and the like, the coking rate of the catalyst is delayed, and the single cycle life of the catalyst is prolonged; in addition, the hydrogen regeneration under specific conditions can completely recover the catalyst activity, and the long-period stable operation of the device is realized.
The production method of the long-chain alkyl aromatic hydrocarbon provided by the invention can be implemented in various reaction devices, such as a fluidized bed, a fixed bed and a slurry bed. In the present invention, the method is carried out using a fixed bed, but the application of the method of the present invention is not limited thereto. The performance of the alkylation reaction was evaluated using both cycle life and product distribution. Wherein the cycle life is based on an olefin conversion of > 99%, the product distribution is based on Linear Alkylbenzene (LAB) and 2-LAB, and the product is analyzed by gas chromatography.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention will be described in detail by way of examples, with the understanding that the embodiments described herein are merely illustrative and explanatory of the invention, and are not intended to limit the scope of the invention.
Example 1
The solid acid catalyst is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division) and alumina according to a weight ratio of 4:1, and loading 0.4wt% of Pt by an impregnation method, wherein the solid acid catalyst is A1, the unit cell constant of the Y-type zeolite is 2.453nm, and the ratio of the mesoporous volume to the total pore volume is 0.22. The solid acid catalyst obtained was numbered A1. The specific physicochemical properties are shown in Table 1.
The alkylation reaction of benzene and n-dodecene is carried out in a fixed bed high pressure micro-reaction experimental apparatus. 5g of solid acid catalyst A1 is filled in a fixed bed reactor with the inner diameter of 10mm and the length of 1m, the reaction temperature is 120 ℃, the reaction pressure is 3Mpa, and the mass space velocity of raw materials is 7h -1 (the molar ratio of benzene was 40).
The single cycle life of the catalyst is determined by the olefin breakthrough time in the product of the alkylation reaction, and the catalyst life refers to the time (h) when the product linear alkylbenzene has a n-dodecene conversion of less than 99% after chromatography.
Alkylation regeneration conditions are shown in Table 2 and multicycle reaction-regeneration results are shown in Table 3. In Table 3, LAB and 2-LAB represent the selectivity of linear alkylbenzene and 2-LAB in the product. The components in the linear alkylbenzene product were analyzed by an on-line chromatograph (GC-7890B of agilent).
Comparative example 1
This comparative example illustrates the alkylation of benzene with n-dodecene using a Pt-free Y-type solid acid catalyst.
The solid acid is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division company) and alumina according to a weight ratio of 4:1, and is marked as B1.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 2
This comparative example is intended to illustrate an alkylation process employing a solid acid catalyst with too high a supported metal content.
The solid acid is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division company) and alumina according to a weight ratio of 4:1, and is marked as B2.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 3
This comparative example is intended to illustrate an alkylation process employing a solid acid catalyst having too low a supported metal content.
The solid acid is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division company) and alumina according to a weight ratio of 4:1, and is marked as B3.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 4
This comparative example is presented to illustrate an alkylation process using a unit cell and a different solid acid catalyst than Kong Zhanbi.
The solid acid is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division company) and alumina according to a weight ratio of 4:1, and is marked as B4.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 5
This comparative example is for illustrating the alkylation process using the solid acid catalyst of the present invention, but at a lower regeneration temperature.
The solid acid was as in example 1.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 6
This comparative example is to illustrate the alkylation process using the solid acid catalyst of the present invention, but at a lower regeneration pressure.
The solid acid was as in example 1.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 7
This comparative example is for illustration of the alkylation process using the solid acid catalyst of the present invention, but with a lower flow of regenerated hydrogen.
The solid acid was as in example 1.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 8
This comparative example is for illustrating the alkylation process using the solid acid catalyst of the present invention, but under conditions where the regeneration rate is too fast.
The solid acid was as in example 1.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
Comparative example 9
This comparative example is intended to illustrate the alkylation process using the solid acid catalyst of the present invention, but with a short regeneration warm-up time.
The solid acid was as in example 1.
The physical and chemical properties of the catalyst are shown in table 1, alkylation regeneration conditions are shown in table 2, and multi-cycle reaction-regeneration results are shown in table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from the data in Table 3, the process for producing long-chain alkylaromatic hydrocarbons using catalysts such as B1, B2, B3, B4 which do not support noble metals or have unsuitable metal contents, is markedly inferior in the initial lifetime of alkylation, lifetime after six regenerations, LAB selectivity and 2-LAB selectivity. In the regeneration step, the conditions such as the regeneration temperature, pressure, hydrogen flow, heating rate, constant temperature time and the like are not in the required range of the invention, and even if the solid acid catalyst is adopted, the alkylation initial life, the life after six times of regeneration, the LAB selectivity and the 2-LAB selectivity are not good; according to the production method of the long-chain alkyl aromatic hydrocarbon, the solid acid catalyst loaded with a proper amount of metal Pt is adopted and regenerated under the hydrogen condition, so that Pt and B acid sites have a strong synergistic catalytic effect, and the catalyst has better alkylation activity and selectivity under the reaction condition provided by the invention, and meanwhile, the hydrogen regeneration has better regeneration activity, so that the long-period stable operation of the catalyst is ensured. For example, when the noble metal Pt content is 0.4%, the catalyst A1 not only has an initial life of 42 hours, but also has a LAB selectivity of 91.2% after six regenerations, and a 2-LAB ratio of 26.2%.
Example 2
This example is intended to illustrate the solid acid alkylation process of the present invention.
The solid acid catalyst is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division) and alumina according to a weight ratio of 4:1, and loading 0.2wt% of Pt by using an impregnation method, wherein the solid acid catalyst is A2, the unit cell constant of the Y-type zeolite is 2.448nm, and the ratio of the mesoporous volume to the total pore volume is 0.15. The solid acid catalyst obtained was numbered A2.
The physical and chemical properties of the catalyst are shown in Table 4, alkylation regeneration conditions are shown in Table 5, and the multi-cycle reaction-regeneration results are shown in Table 6.
Example 3
This example is intended to illustrate the solid acid alkylation process of the present invention.
The solid acid catalyst is prepared by uniformly mixing Y-type zeolite (purchased from China petrochemical catalyst division) and alumina according to a weight ratio of 4:1, and loading 2wt% of Pt by an impregnation method, wherein the solid acid catalyst is A3, the unit cell constant of the Y-type zeolite is 2.457nm, and the ratio of the mesoporous volume to the total pore volume is 0.29. The solid acid catalyst obtained was numbered A3.
The physical and chemical properties of the catalyst are shown in Table 4, alkylation regeneration conditions are shown in Table 5, and the multi-cycle reaction-regeneration results are shown in Table 6.
TABLE 4 Table 4
TABLE 5
TABLE 6
Claims (10)
1. A process for preparing long-chain alkyl aromatic hydrocarbon includes such steps as preparing long-chain olefinAnd the alkylation reaction process of the aromatic hydrocarbon and the regeneration process of the solid acid catalyst, wherein in the alkylation reaction process of the long-chain olefin and the aromatic hydrocarbon, the alkylation reaction condition is that the temperature is 90-180 ℃, the pressure is 2.0-4.5 MPa, and the raw material mass airspeed is 1-30 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The solid acid catalyst is Y-type zeolite loaded with hydrogenolysis metal components, the unit cell of the Y-type zeolite is 2.448-2.457 nm, the ratio of the mesoporous volume to the total pore volume is 0.15-0.29, and the hydrogenolysis metal components account for 0.15-5wt% of the solid acid catalyst; the regeneration process of the solid acid catalyst is to heat the solid acid catalyst to 300-460 ℃ in a hydrogen atmosphere at a heating rate of 1-15 ℃/min and treat the solid acid catalyst for at least 5 hours under the conditions of the temperature and 1.5-3MPa and a hydrogen flow of 150-500 mL/min/g.
2. The method of claim 1, wherein the solid acid catalyst further comprises an inorganic oxide matrix.
3. The method of claim 2, wherein the inorganic oxide is selected from one or more of the group consisting of silica, alumina, zirconia and titania.
4. The process according to claim 1, wherein the Y zeolite is present in an amount of 40 to 95 wt.%, based on the solid acid catalyst.
5. A process according to claim 1, characterized in that the Y zeolite has a unit cell of 2.452 to 2.455nm.
6. The process according to claim 1, wherein the ratio of the mesoporous volume to the total pore volume of the Y-zeolite is from 0.18 to 0.26.
7. The process according to claim 1, wherein the hydrogenolytic metals are selected from one or more of group VIB, VIIB and VIII metals.
8. The method of claim 7 wherein the group VIII metal is selected from one or more of Pt, pd, and Ru.
9. The process according to claim 1, characterized in that the hydrogenolytic metals comprise 0.2 to 2wt%, preferably 0.4 to 1wt%, of the solid acid catalyst.
10. The process according to claim 1, characterized in that the regeneration of the solid acid catalyst is carried out when the conversion of long-chain olefins is < 99% during the alkylation of long-chain olefins with aromatic hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211059250.3A CN117658758A (en) | 2022-08-31 | 2022-08-31 | Production method of long-chain alkyl aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211059250.3A CN117658758A (en) | 2022-08-31 | 2022-08-31 | Production method of long-chain alkyl aromatic hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117658758A true CN117658758A (en) | 2024-03-08 |
Family
ID=90066841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211059250.3A Pending CN117658758A (en) | 2022-08-31 | 2022-08-31 | Production method of long-chain alkyl aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117658758A (en) |
-
2022
- 2022-08-31 CN CN202211059250.3A patent/CN117658758A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4432019B2 (en) | Method for producing aromatic hydrocarbon compound and liquefied petroleum gas from hydrocarbon raw material | |
| JP5110316B2 (en) | Process for producing aromatic hydrocarbons and liquefied petroleum gas from hydrocarbon mixtures | |
| TWI316541B (en) | Process for reducing bromine index of hydrocarbon feedstocks | |
| CN103121906B (en) | Method for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon | |
| CN107754845B (en) | Long-life catalyst for reducing olefins in reformate | |
| KR100776468B1 (en) | Improved zeolites and molecular sieves and the use thereof | |
| TWI306894B (en) | Process for reducing bromine index of hydrocarbon feedstocks | |
| EP2690160A1 (en) | Method for producing single-ring aromatic hydrocarbons | |
| WO2007135769A1 (en) | Process for producing hydrocarbon fraction | |
| JP2007154151A (en) | Method for producing 6-8c aromatic hydrocarbon | |
| Tsai et al. | Metal zeolites for transalkylation of toluene and heavy aromatics | |
| JP2009235247A (en) | Method for producing aromatic hydrocarbon having six to eight carbon atoms | |
| CN113881457A (en) | Method for treating distillate oil rich in aromatic hydrocarbon | |
| CN110653003B (en) | Solid acid catalyst, preparation method and alkylation reaction method thereof | |
| WO2020050092A1 (en) | Method for producing xylene | |
| CN117658758A (en) | Production method of long-chain alkyl aromatic hydrocarbon | |
| CN117654648A (en) | Regeneration method of solid acid catalyst for synthesizing long-chain alkyl aromatic hydrocarbon | |
| CN117654591A (en) | Synthesis method of straight-chain alkyl aromatic hydrocarbon | |
| JP2020500710A (en) | Catalyst system and method for converting hydrocarbon feed utilizing said catalyst system | |
| KR20190030709A (en) | Process for the production of lower olefins and monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms, production of lower olefins and monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms | |
| CN117658757A (en) | Alkylation reaction method of aromatic hydrocarbon and long-chain olefin | |
| JPH0782176A (en) | Quality improving method for paraffin supply material | |
| US11845705B2 (en) | Processes integrating hydrocarbon cracking with metathesis for producing propene | |
| CN117654592A (en) | Solid acid catalyst and production method of long-chain alkyl aromatic hydrocarbon | |
| CN112694912B (en) | Naphtha modification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |