CN100497272C - Method for producing phenyl-alkane by using olefin isomerization and paraffin recirculation - Google Patents
Method for producing phenyl-alkane by using olefin isomerization and paraffin recirculation Download PDFInfo
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- CN100497272C CN100497272C CNB2003801110028A CN200380111002A CN100497272C CN 100497272 C CN100497272 C CN 100497272C CN B2003801110028 A CNB2003801110028 A CN B2003801110028A CN 200380111002 A CN200380111002 A CN 200380111002A CN 100497272 C CN100497272 C CN 100497272C
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- phenyl
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- isomerization
- monoolefine
- phenyl alkanes
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- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 131
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 62
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 phenyl compound Chemical class 0.000 claims abstract description 145
- 238000000034 method Methods 0.000 claims abstract description 84
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 79
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 71
- 230000029936 alkylation Effects 0.000 claims abstract description 66
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 4
- 239000003879 lubricant additive Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 128
- 229910052799 carbon Inorganic materials 0.000 claims description 104
- 239000000463 material Substances 0.000 claims description 100
- 229930195733 hydrocarbon Natural products 0.000 claims description 73
- 150000002430 hydrocarbons Chemical class 0.000 claims description 69
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 18
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 238000007600 charging Methods 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000006277 sulfonation reaction Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000005673 monoalkenes Chemical class 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 4
- 230000002152 alkylating effect Effects 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000003599 detergent Substances 0.000 abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 150000003871 sulfonates Chemical class 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 description 65
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000001131 transforming effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001260 acyclic compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000021322 Vaccenic acid Nutrition 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LTXREWYXXSTFRX-QGZVFWFLSA-N Linagliptin Chemical compound N=1C=2N(C)C(=O)N(CC=3N=C4C=CC=CC4=C(C)N=3)C(=O)C=2N(CC#CC)C=1N1CCC[C@@H](N)C1 LTXREWYXXSTFRX-QGZVFWFLSA-N 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical compound [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- JTOGFHAZQVDOAO-UHFFFAOYSA-N henicos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCC=C JTOGFHAZQVDOAO-UHFFFAOYSA-N 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000011064 split stream procedure Methods 0.000 description 1
- 230000005477 standard model Effects 0.000 description 1
- ZDLBWMYNYNATIW-UHFFFAOYSA-N tetracos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC=C ZDLBWMYNYNATIW-UHFFFAOYSA-N 0.000 description 1
- SJDSOBWGZRPKSB-UHFFFAOYSA-N tricos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCC=C SJDSOBWGZRPKSB-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
- C07C309/31—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups by alkyl groups containing at least three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
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- 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
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for producing phenyl-alkanes by paraffin dehydrogenation followed by olefin isomerization and then by alkylation of a phenyl compound by a lightly branched olefin is disclosed. An effluent of the alkylation section comprises paraffins that are recycled to the dehydrogenation step. A process that sulfonates phenyl-alkanes having lightly branched aliphatic alkyl groups to produce modified alkylbenzene sulfonates is also disclosed. In addition, the compositions produced by these processes, which can comprise detergents, lubricants, and lubricant additives, are disclosed.
Description
Background of invention
The present invention relates generally to the alkylation of the use solid catalyst of phenyl compound and alkene, and more specifically to a kind of method of using the solid alkylation catalyst selectivity to produce specific phenyl alkanes.
Before about three more than ten years, many household laundry washing composition are to be made by branched-alkyl benzene sulfonate (BABS).BABS is by the class alkylbenzene preparation that is called branched-alkyl benzene (BAB).Alkylbenzene (phenyl alkanes) refers to have and is bonded to the aliphatic alkyl on the phenyl and has general formula (m
i-alkyl
i)
iOne big compounds of-n-phenyl alkanes.Aliphatic alkyl is by at general formula (m
i-alkyl
i)
iThe aliphatic alkyl chain that is called as " alkane " in-n-phenyl alkanes is formed.In the aliphatic alkyl chain, the aliphatic alkyl chain is the long linear with the carbon that is bonded on the phenyl.Aliphatic alkyl can also comprise one or more alkyl branches, and each of described alkyl branches all is connected to the aliphatic alkyl chain and at (m
i-alkyl
i)
iIn-n-phenyl alkanes the general formula by corresponding " (m
i-alkyl
i)
i" expression.
The feature description of BAB is in US-A-6, among 187,981 B1.In brief, the primary carbon atom that each aliphatic alkyl of BAB has greater number, the phenyl among the BAB can be connected on any non-primary carbon atom of aliphatic alkyl chain, and one of the carbon of the aliphatic alkyl of BAB is that quaternary carbon has higher possibility.
When the carbon atom on the alkyl chain was connected on the carbon atom of the carbon atom of two other carbon on the alkyl group side chain, alkyl branches and phenyl, resulting alkyl phenyl alkane was called " season alkyl phenyl alkane " or abbreviates " quat " as.Therefore, quat comprises the alkyl phenyl alkane of general formula m-alkyl-m-phenyl alkanes.If quaternary carbon is second carbon atom from the end of alkyl group side chain, then resulting 2-alkyl-2-phenyl alkanes is called " terminal quat ".Any other quaternary carbon along alkyl group side chain is called " inner quat ".
Before 30 years by the household laundry detergent pollution of BABS preparation river and lake.Solved this problem by linear alkylbenzene sulfonate (LABS) preparing washing agent than the faster degraded of BABS.LABS is by the alkylbenzene preparation that is called linear alkylbenzene (LAB).US-A-6,187,981B1 has described LAB.LAB has the linear aliphatic alkyl that has two primary carbon atoms, and the phenyl among the LAB is typically connected on any secondary carbon(atom) of linear aliphatic alkyl.
Some modified alkylbenzene sulfonates has been determined in research recently, and this paper is called MABS.MABS is different from BABS and compares the efficient with excellence in improved laundry spatter property, hard-surface cleaning and the hard water with the LABS alkylbenzene sulfonate and with LABS on forming, also have biological degradability simultaneously.The alkylbenzene of sulfonation modifying (MAB) will be produced MABS.MAB comprises the phenyl alkanes of the aliphatic alkyl of slight branching and phenyl and has general formula (m
i-alkyl
i)
i-n-phenyl alkanes.MAB has two, three or four primary carbons usually, contains a high proportion of 2-phenyl alkanes, and has the inside quat of low ratio.US-A-6,187,981 B1 disclose a kind of method of producing MAB under the situation of paraffinic hydrocarbons recirculation by isomerization of paraffinic hydrocarbons, paraffin dehydrogenation and alkylation.US-A-5,276,231 have described to prepare the method for LAB and disclose under a kind of situation of the aromatic hydrocarbons by product of removing the paraffin dehydrogenation district in selectivity paraffinic hydrocarbons have been recycled to dehydrogenation zone, make any monoolefine selective hydrogenation in the paraffinic hydrocarbons recycle stream and make diolefine by product selective hydrogenation from dehydrogenation zone.
For producing unique slight branching or removing other alkylation and the adsorption separating method of straight chain alkylbenzene, referring to PCT international open WO 99/05082, WO99/05084,99/05241, WO99/05243 and WO99/07656, this paper is incorporated herein by reference hereby.
Because MABS is better than other alkylbenzene sulfonate, thereby research has the Catalyst And Method that required optionally selectivity is produced MAB to the 2-phenyl alkanes with to inside season phenyl alkanes.
Summary of the invention
The invention discloses a kind of method of producing phenyl alkanes, particularly modified alkylbenzene (MAB) by the alkylating step of paraffin dehydrogenation, isomerisation of olefin and phenyl compound, wherein the paraffinic hydrocarbons that alkylation is flowed out in the thing is recycled to dehydrogenation step.The paraffinic hydrocarbons of recirculation can be straight chain or non-linear paraffins, comprises the paraffinic hydrocarbons of slight branching.Because the paraffinic hydrocarbons of recirculation can be converted into the alkene of slight branching, this method has reclaimed alkylation effectively and has flowed out the paraffinic hydrocarbons in the thing and use it for the useful phenyl alkanes product of production.Therefore, for the paraffinic feedstock of the setting dosage that is fed to this method, this method has improved the productive rate of useful products, avoided simultaneously after paraffin dehydrogenation step and before alkylation step from monoolefine the difficulty of disengaging latch alkane.
When being used for detergent alkylate, this method is produced washing composition, and described washing composition satisfies the requirement for the optionally increasingly stringent of 2-phenyl alkanes selectivity of producing modified alkylbenzene (MAB) and inside season phenyl alkanes.Therefore, the MAB sulfonation is compared with production with linear alkylbenzene sulfonate and had the modification linear alkylbenzene sulfonate (MABS) that cleans validity and biological degradability in improved hard water and/or the cold water.
It is believed that the MAB and the MABS that produce by method disclosed herein are not the products of producing by the method for prior art, the transforming degree that the method for prior art does not make paraffinic hydrocarbons recirculation and the transforming degree of branched paraffin can surpass the transforming degree of (straight chain) paraffinic hydrocarbons just and/or heavy paraffins in dehydrogenation zone may surpass the transforming degree of light paraffins.In this case and since equilibrium-limited the transforming degree of paraffinic hydrocarbons, the dehydrogenation zone effluent can comprise more straight chain and/or light paraffins.Therefore, can improve the concentration of linear paraffins in the recirculation paraffin stream and/or light paraffins.And this can improve the concentration of linear paraffins in the dehydrogenation zone and/or light paraffins and the final transformation efficiency that improves linear paraffins and/or light paraffins and removes the ingress rate that speed equals to enter from those paraffinic hydrocarbonss of paraffinic feedstock and recirculation paraffin stream dehydrogenation zone through dehydrogenation and alkylation subsequently until linear paraffins and/or light paraffins from technology.Therefore, for for conversion of olefines degree given in the alkylation zone, the aliphatic alkyl chain of MAB product of the present invention will keep the carbon number similarity bigger to paraffinic feedstock than the method for prior art.Compare with the present invention, the method for prior art makes the higher carbon number of aliphatic alkyl intrachain carbon number distribution deflection of MAB.When sulfonation, MABS product of the present invention is tending towards keeping the carbon number distribution with the similar aliphatic alkyl chain of paraffinic feedstock.Therefore, for given feed composition, method of the present invention can be produced the specific MAB and the MABS product of the method that is different from prior art, and described product has the aliphatic alkyl chain of specific degree of branching.
In sum, the present invention includes following content:
1, a kind of method of producing phenyl alkanes, this method comprises the steps:
A) make the charging dehydrogenation that comprises the C8-C28 paraffinic hydrocarbons in the part of the dehydrogenation under operating in the dehydrogenation condition that is enough to make paraffin dehydrogenation, and from the partially recycled dehydrogenation product materials flow that comprises monoolefine and paraffinic hydrocarbons of dehydrogenation;
B) materials flow of near small part dehydrogenation product is delivered in the isomerization part that operates under the isomerisation conditions that is enough to make isomerisation of olefin, and from the partially recycled isomerization product materials flow that comprises monoolefine and paraffinic hydrocarbons of isomerization, wherein the monoolefine in the isomerization product materials flow has 8-28 carbon atom, and wherein has 3 or 4 primary carbon atoms and do not have quaternary carbon atom to the small part monoolefine in the dehydrogenation product materials flow;
C) deliver to the alkylation part with phenyl compound with to the isomerization product materials flow that small part comprises monoolefine, be enough to adopt monoolefine making under the alkylating alkylation conditions of phenyl compound operation alkylation part in the presence of the alkylation catalyst to form phenyl alkanes, described phenyl alkanes comprises such molecule, be that it has a phenyl moiety and an aliphatic alkyl part, it comprises 8-28 carbon atom; Wherein except any quaternary carbon atom of the carbon atom keyed jointing by C-C and phenyl moiety, what form in the alkylation part has 2,3 or 4 primary carbon atoms and does not have quaternary carbon atom to the small part phenyl alkanes; And wherein alkylation is 40-100 to the selectivity of 2-phenyl alkanes, and the selectivity of inside season phenyl alkanes is less than 10;
D) from the partially recycled recycle stream that comprises the alkylate materials flow of phenyl alkanes and comprise paraffinic hydrocarbons of alkylation; With
E) near small part recycle stream is delivered to the dehydrogenation part.
2, the method for project 1, it is further characterized in that to the materials flow of small part dehydrogenation product and to the materials flow of small part isomerization product at least one and comprises the monoolefine of slight branching and preferably be higher than to the 25mol% of small part isomerization product materials flow to the concentration of the monoolefine of the slight branching of small part isomerization product materials flow.
3, the method for project 2, it is further characterized in that comprising straight chain mono-olefins and preferably be less than or equal 75mol% to the concentration of the straight chain mono-olefins of small part isomerization product materials flow to the small part monoolefine to materials flow of small part isomerization product and to the materials flow of small part dehydrogenation product at least one.
4, the method for project 2, it is further characterized in that having at least one quaternary carbon atom and preferably being less than 10mol% to the concentration of the alkene that contains at least one quaternary carbon atom of small part isomerization product materials flow to the small part monoolefine to materials flow of small part dehydrogenation product and to the materials flow of small part isomerization product at least one.
5, the method for project 1, wherein the weight in average of the aliphatic alkyl of the phenyl alkanes of phenyl alkanes is between the weight of C10 aliphatic alkyl and C13 aliphatic alkyl; The content that phenyl is connected to the phenyl alkanes of the 2-of aliphatic alkyl and/or 3-position is higher than 55 weight % of phenyl alkanes; When the summation of the content of 2-phenyl alkanes and 3-phenyl alkanes is higher than 55 weight % of phenyl alkanes and is less than or when equaling 85 weight %, the average branching level of the aliphatic alkyl of phenyl alkanes is 0.25-1.4 alkyl of each phenyl alkanes molecule, or when the concentration summation of 2-phenyl alkanes and 3-phenyl alkanes was higher than 85 weight % of phenyl alkanes, the average branching level of the aliphatic alkyl of phenyl alkanes was 0.4-2.0 alkyl of each phenyl alkanes molecule; The aliphatic alkyl of phenyl alkanes comprises the aliphatic alkyl of linear aliphatic alkyl, single branching or the aliphatic alkyl of two branching; If present, the alkyl branches on the aliphatic alkyl chain of aliphatic alkyl comprises methyl branch, ethyl branch or propyl group side chain; And if present, alkyl branches is connected on any position of aliphatic alkyl chain of aliphatic alkyl, condition be the aliphatic alkyl that has at least one quaternary carbon atom on the phenylalkyl constitute phenyl alkanes be less than 20%.
6, the method for project 1, it is further characterized in that dehydrogenation partly comprises dehydrogenation catalyst, described dehydrogenation catalyst comprises at least a VIII (IUPAC 8-10) family's metal and is dispersed in the outer interior promoter metal of the inorganic oxide that is attached on the refractory inorganic oxide, and described catalyzer comprises kernel and further is dispersed with the dehydrogenation catalyst of properties-correcting agent metal thereon.
7, the method for project 1, it is further characterized in that isomerization partly comprises isomerization catalyst, described isomerization catalyst comprises the solid support material that is selected from ferrierite, SAPO-11 and MgAPSO-31.
8, the method for project 1, it is further characterized in that isomerization partly comprises isomerization catalyst, and described isomerization catalyst comprises VIII (IUPAC 8-10) family's metal and isomerization part operation, and to be higher than 0.01:1 and temperature in the mol ratio that comprises hydrogen/hydrocarbon be under 50-400 ℃ the isomerisation conditions.
9, the method for project 1, it is further characterized in that alkylation catalyst comprises the zeolite with the zeolite structure type that is selected from BEA, MOR, MTW and NES.
10, the method for project 1, wherein monoolefine comprises monomethyl alkene and phenyl alkanes comprises monomethyl-phenyl alkanes.
11, the method for project 1, it is further characterized in that to the monoolefine concentration of small part recycle stream and is less than 0.3 weight %.
12, a kind of modified alkylbenzene composition, wherein modified alkylbenzene is by each method production among the project 1-11.
13, according to the modified alkylbenzene composition of project 12, wherein the modified alkylbenzene composition comprises lubricant or lubricant additive.
14, each method among the project 1-11, it is further characterized in that under the sulfonation condition of the sulfonated products materials flow that is enough to make phenyl alkanes sulfonation and production comprise phenyl alkanes sulfonic acid partially alkylated at least product materials flow is contacted with sulphonating agent, and is being enough under the neutrality condition that makes the neutralization of phenyl alkanes sulfonic acid and produce the neutralized reaction product materials flow that comprises phenyl alkanes sulfonate partly sulfonated at least product materials flow to be contacted with neutralizing agent.
15, a kind of modified alkylbenzene sulfonates composition, wherein modified alkylbenzene sulfonates is by the method production of project 14.
Detailed Description Of The Invention
Two kinds of chargings of Xiao Haoing are paraffin compound and phenyl compound in the method for the invention.Paraffinic feedstock can comprise that the total carbon atom number that each paraffin molecules has is 8-28, and is 8-15 in other embodiments, 10-15, and non-branching of 11-13 carbon atom (straight chain) or n-paraffin molecule.Two carbon atoms of each non-branching paraffin molecules are that primary carbon atom and remaining carbon atom are secondary carbon(atom).
Except the non-branching paraffinic hydrocarbons, also other open chain compound can be fed in the method for the present invention.Described other open chain compound can be fed in the method for the present invention in the paraffinic feedstock that contains the non-branching paraffinic hydrocarbons, or one or more other materials flows through being fed to method of the present invention are fed in the method for the present invention.A kind of this type of open chain compound is the paraffinic hydrocarbons of slight branching, as used herein, the paraffinic hydrocarbons of described slight branching refers to has the paraffinic hydrocarbons that total carbon atom number is 8-28, and wherein three or four carbon atom are that primary carbon atom and remaining carbon atom all are not quaternary carbon atoms.The paraffinic hydrocarbons of slight branching can have and adds up to 8-15 carbon atom, and 10-15 carbon atom in another embodiment, and in another embodiment 11-13 carbon atom.It is (p that the paraffinic hydrocarbons of slight branching generally includes general formula
i-alkyl
i)
iThe aliphatic alkanes of-alkane.The paraffinic hydrocarbons of slight branching comprises the long linear aliphatic alkyl chain of the paraffinic hydrocarbons of slight branching, at (p
i-alkyl
i)
iBe known as in-the alkane " alkane ".The paraffinic hydrocarbons of slight branching also comprises one or more by corresponding " (p
i-alkyl
i)
i-" expression alkyl branches, wherein subscript " i " equals the number of alkyl branches and the carbon number p of each corresponding alkyl branches and aliphatic alkyl chain
iRelevant.The aliphatic alkyl chain is along the direction of the carbon atom with alkyl branches that may the produce minimum numeral numbering that passes through.
The alkyl branches of the paraffinic hydrocarbons of slight branching can be selected from methyl, ethyl and propyl group, preferably than lacking and being the side chain of positive structure.Paraffinic hydrocarbons with slight branching of two alkyl branches or four primary carbon atoms can constitute total slight branching paraffinic hydrocarbons be less than 40mol%, and be less than 25mol% in another embodiment.Paraffinic hydrocarbons with slight branching of an alkyl branches or three primary carbon atoms can constitute total slight branching monoolefine more than 70mol%.Any alkyl branches can be keyed on any carbon on the aliphatic alkyl chain.
Process feeds can comprise than the more highly branched paraffinic hydrocarbons of the paraffinic hydrocarbons of slight branching.But when dehydrogenation, described highly branched paraffinic hydrocarbons is tending towards forming highly branched monoolefine, and described monoolefine is tending towards forming BAB when alkylation.For example, the paraffin molecules that comprises at least one quaternary carbon atom is in dehydrogenation, is tending towards forming the phenyl alkanes with quaternary carbon atom during alkylation subsequently and do not relate to phenyl.The inlet amount of these highly branched paraffinic hydrocarbonss that are fed to this technology is minimized.In mol, all paraffinic hydrocarbonss that contain the paraffin molecules of at least one quaternary carbon atom or be fed to this technology in paraffinic feedstock usually constitute and are less than 10%, preferably are less than 5%, more preferably less than 2%, and most preferably are less than 1%.
Paraffinic feedstock is generally the mixture of the paraffinic hydrocarbons of straight chain with different carbon numbers or slight branching.Can use any method that is suitable for the production paraffinic feedstock.The hydrocarbon of a kind of method by from kerosene boiling range petroleum fractions, separating non-branching (straight chain) or the hydrocarbon production paraffinic feedstock of slight branching.Checked that to be used for described isolating commercial run be UOP ' s Molex from isoparaffin and naphthenic hydrocarbon liquid phase adsorption separation n-paraffin
TMTechnology and from non-n-paraffin UOP ' the s Kerosene Isosiv of Gas Phase Adsorption separation of normal paraffins
TMTechnology.The feed steam of above-mentioned separating technology comprises the branched paraffin more highly branched than the paraffinic hydrocarbons of slight branching.
Known analytical procedure can be determined the composition of mixture of the paraffinic hydrocarbons of the described straight chain for the feed steam of paraffinic feedstock or above-mentioned adsorptive separation technology, slight branching and branching in the gas-chromatography field.From the 315th page of beginning of Chromatographia 1,1968, H.Schulz etc. have described the temperature programmed gas chromatography of the component in the complex mixture that is suitable for confirming paraffinic hydrocarbons.
For detergent alkylation, the phenyl compound of phenyl charging comprises benzene.The phenyl compound of phenyl charging can be alkylation or other substitutive derivative that is higher than the molecular weight of benzene, comprise toluene, ethylbenzene, dimethylbenzene, phenol, naphthalene or the like, but compare with alkylated benzenes, these alkylates may be more unaccommodated detergent precursors.
Method of the present invention can be divided into dehydrogenation part, isomerization part and alkylation part.The present invention is not limited to any specific flow process for the dehydrogenation part.The dehydrogenation part can mainly adopt US-A-6, and mode disposes described in 187,981 B1.Can use any suitable dehydrogenation catalyst.Catalyzer can be to comprise kernel and the outer field laminar composition that is attached on the kernel, its mesectoderm is included in refractory inorganic oxide and at least a promoter metal that homodisperse on it has at least a platinum family (group VIII (IUPAC8-10)) metal, and at least a properties-correcting agent metal is dispersed on the catalyst composition.Skin is less than the degree of 10 weight % in conjunction with kernel to abrasion loss, based on outer field weight.Described catalyzer is described in US-A-6, in 177,381.Dehydrogenation condition is selected so that cracking and polyolefine by product minimize.
Although under dehydrogenation condition olefin skeletal isomerization may take place, the olefin skeletal isomerization in the dehydrogenation part is not requirement of the present invention, because make isomerisation of olefin in aftermentioned isomerization part.Reducing desorption temperature can make skeletal isomerization minimize.The skeletal isomerization meaning under dehydrogenation condition is the isomerization that increases the primary carbon atom number of paraffinic hydrocarbons or olefin hydrocarbon molecules.From paraffin dehydrogenation part the dehydrogenation product materials flow that contains monoolefine normally on the skeleton corresponding to the unreacted paraffinic hydrocarbons of the paraffinic hydrocarbons that is fed to the dehydrogenation part and the mixture of alkene.The skeletal isomerization meaning of the paraffinic hydrocarbons of minimum and alkene is to be less than 15mol% in the dehydrogenation part, preferably is less than paraffinic hydrocarbons and the olefin skeletal isomerization of 10mol%.Therefore, preferably when most of feeding chain alkane were straight chain (not branching), most of alkene were the alkene of straight chain (not branching).
Straight chain mono-olefins in the dehydrogenation reaction effluent enters the skeletal isomerization district, the primary carbon atom number that this has reduced linearity and has regulated olefin hydrocarbon molecules.The skeletal isomerization of molecule can comprise that aliphatic chain increases by 1 or 2 methyl branch.Because it is identical that the total number of carbon atoms of olefin hydrocarbon molecules keeps, thereby each adds methyl branch and causes aliphatic chain to reduce by a carbon.
The skeletal isomerization step effectively reduces the linearity of dehydrogenation reaction effluent, so that after being used for alkylation, the phenyl alkanes alkylide satisfies primary carbon atom, 2-phenyl alkanes selectivity and the optionally requirement of inner season phenyl alkanes.The skeletal isomerization of raw material olefin can adopt mode well known by persons skilled in the art and any known catalyzer to realize.The catalyzer that is fit to comprises ferrierite, ALPO-31, SAPO-11, SAPO-41, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41, lomontite, cancrinite, offretite, the stillbite of hydrogen form, the partheite of the mordenite of magnesium or calcium form and magnesium or calcium form.The MeAPSO-31 catalyzer that is fit to comprises MgAPSO-31.Many natural zeolites with initial reduction aperture, for example ferrierite can be converted into the type that is suitable for olefin skeletal isomerization to produce basic hydrogen form by removing the basic metal or the alkaline-earth metal that link to each other with ammonium ion exchange with calcining, as US-A-4,795,623 and US-A-4, instruct in 924,027.But H shape mordenite is not the catalyzer that is suitable for the skeletal isomerization of olefin feedstock.The skeletal isomerization of olefin feedstock is disclosed in US-A-5 with catalyzer and condition, and 510,306; US-A-5,082,956; And US-A-5, in 741,759.The skeletal isomerization condition is included in the condition of the part or all of at least hydrocarbon contact skeleton isomerization catalyst in the liquid phase.Isomerisation temperature is 50-400 ℃ (122-752 ℉).When isomerization catalyst contained VIII (IUPAC 8-10) family metal, isomerisation conditions comprised that the mol ratio of hydrogen/hydrocarbon is greater than 0.01:1.
The isomerization product materials flow that is used to produce MAB contains the monoolefine of slight branching.The monoolefine of slight branching refers to the monoolefine that total carbon atom number is 8-28, wherein three or four carbon atom be that primary carbon atom and remaining carbon atom all are not quaternary carbon atom.The monoolefine of slight branching can have the 8-15 of ading up to carbon atom, preferred 10-15 carbon atom, and more preferably 11-13 carbon atom.The concentration of the monoolefine of the slight branching of isomerization product materials flow is greater than 25mol%.
It is (p that the monoolefine of slight branching generally includes general formula
i-alkyl
i)
iThe aliphatic olefin of-q-alkene, long linear aliphatic series thiazolinyl contains the carbon-to-carbon double bond by " alkene " indication.The monoolefine of slight branching comprises also that one or more and aliphatic alkenylene chain links to each other and by " (p accordingly in the formula
i-alkyl
i)
i" alkyl branches of indication.Two keys are at the carbon number q of aliphatic alkenylene chain and (q+1).The aliphatic series alkenylene chain is numbered from an end along the direction of the carbon atom with two keys that produces lowest number.
The monoolefine of slight branching can be α monoolefine or vinylidene monoolefine, but monoolefine in preferred.As used herein, term " alhpa olefin " refers to formula R-CH=CH
2Alkene.As used herein, term " internal olefin " comprises that two of formula R-CH=CH-R replaces four substituted olefines that three of internal olefin, formula R-C (R)=CH-R replaces internal olefin and formula R-C (R)=C (R)-R.Two replace internal olefin comprises formula R-CH=CH-CH
3The β internal olefin.As used herein, term " vinylidene alkene " refers to formula R-C (R)=CH
2Alkene.In preceding formula, R be with each formula in the identical or different alkyl of other alkyl.In the scope that definition allowed of term " internal olefin ", when the monoolefine of slight branching was interior monoolefine, any two carbon atoms of aliphatic alkenylene chain can have two keys.The monoolefine of the slight branching that is fit to comprises octene, nonene, decene, undecylene, dodecylene, tridecylene, tetradecene, 15 carbenes, cetene, heptadecene, vaccenic acid, 19 carbenes, eicosylene, heneicosene, two dodecylenes, tricosene, tetracosene, ppentacosene, cerotene, cerotene and two vaccenic acids.
The alkyl branches of the monoolefine of usually slight branching is methyl, ethyl and propyl group, preferably the side chain of short and positive structure.Preferably, the monoolefine of slight branching only has an alkyl branches, but also can have two alkyl branches.Monoolefine with slight branching of two alkyl branches or four primary carbon atoms constitute total slight branching monoolefine be less than 40mol%, and preferably be less than 30mol%, the monoolefine of remaining slight branching has an alkyl branches.Monoolefine with slight branching of an alkyl branches or three primary carbon atoms constitute total slight branching monoolefine more than 70mol%.US-A-6,187,981 have described the analytical procedure of the composition of the monoolefine mixture of determining slight branching.
Except the monoolefine of slight branching, other acyclic compound also can contact alkylation catalyst.Isomerization product materials flow or one or more other materials flows can make described acyclic compound contact with catalyzer.Other acyclic compound comprises the alkene and the monoolefine of non-branching (straight chain), comprises the paraffinic hydrocarbons of straight chain or non-straight chain.Can contact the total carbon atom number that each paraffin molecules of alkene of the non-branching (straight chain) of zeolite has is 8-28, preferred 8-15, and more preferably 10-14 carbon atom.The alkene of non-branching can be the α monoolefine, but is preferably interior monoolefine.When in the isomerization product materials flow and the monoolefine of slight branching when existing together, normal olefine content preferably is less than or equals the 75mol% of total monoolefine in the isomerization product materials flow, and more preferably less than the 60mol% of total monoolefine.
Owing to may there be straight chain mono-olefins, the monoolefine molecule in each isomerization product materials flow of most of isomerization product materials flow can on average comprise and be less than 3, or 3-4 primary carbon atom.According to the relative proportion of straight chain with the monoolefine of slight branching, the summation of all monoolefines of isomerization product materials flow or contact zeolite can have 2.25-4 primary carbon atom/monoolefine molecule.
If any, can or not contact the straight chain of zeolite and/or total carbon atom number that each paraffin molecules of non-linear paraffins can have is a 8-28 carbon atom, preferred 8-15 carbon atom, and more preferably 10-14 carbon atom through isomerization product materials flow contact.This type of straight chain and the expectation of non-linear paraffins are not significantly disturbed alkylation step but are used as thinner.But, in alkylation reactor, exist this type of thinner to cause higher process stream volumetric flow rate usually, this needs bigger equipment and more catalyzer and bigger product retrieving arrangement in the alkylated reaction circuit.The isomerization product materials flow does not preferably contain the impurity or the poisonous substance of unacceptable concentration, and described impurity or poisonous substance cause difficulty in alkylation step.Known step is for example removed by distillation and with selective hydrogenation polyolefine is converted into monoolefine and can removes some impurity.When making phenyl compound with the alkene monoalkylation of slight branching, the isomerization product materials flow preferably contains the dipolymer of the alkene of (if any) specific slight branching hardly.
The concentration of monoolefine more highly branched than the monoolefine of slight branching in the isomerization product materials flow is minimized to avoid it to be converted into BAB when the alkylation.For example, the isomerization product materials flow can contain the monoolefine molecule with at least one quaternary carbon atom, and described monoolefine molecule is tending towards forming the phenyl alkanes with quaternary carbon atom when alkylation, described quaternary carbon atom not with the phenyl moiety keyed jointing.Monoolefine with at least two quaternary carbon atoms preferably constitute isomerization product materials flow or contact catalyst all monoolefine summations be less than 10mol%, and more preferably less than 1mol%.
The product of skeletal isomerization step contains the monoolefine of slight branching and can partly provide alkene to alkylation.Therefore, the isomerization product materials flow can be mainly to be that (it is usually at C for unreacted paraffins, straight chain (non-branching) alkene and branching monoolefine
8-C
28In the scope, preferably at C
8-C
15In the scope and more preferably at C
10-C
15In the scope) mixture.The 20-60mol% of total monoolefine is straight chain (non-branching) alkene in the isomerization product materials flow.The alkene of monoalkyl branching is preferably monomethyl alkene in the isomerization product materials flow.In three embodiments of the present invention, the olefin(e) centent of the dialkyl group branching of isomerization product materials flow is the 30mol% that is less than of isomerization product materials flow, 10mol%-20mol% and be less than 10mol%.The isomerization product materials flow can be formed by the product of the part or the skeletal isomerization step of aliquot portion.The aliquot portion of the product of skeletal isomerization step is the part that has basically with the skeletal isomerization product of the product same composition of skeletal isomerization step.
Except isomerisation of olefin, the paraffinic hydrocarbons skeletal isomerization also can take place in the isomerisation of olefin part.By described alkylation part thereafter and be recycled to the dehydrogenation part, they mix with paraffinic hydrocarbons from paraffinic feedstock any non-linear paraffins that obtains in described dehydrogenation part with (straight chain) paraffinic hydrocarbons just in the isomerization product materials flow.In the dehydrogenation part, the non-linear paraffins of these recirculation can or can not dehydrogenation be a monoolefine.These isomerized paraffinic hydrocarbonss or enter the isomerisation of olefin part once more as the alkene of isomerized paraffin conversion then, wherein they can carry out further isomerization.Therefore, the isomerization product materials flow contains the non-straight chain alkene that can repeatedly be produced by dehydrogenation, isomerization and alkylation part by paraffinic hydrocarbons and the mixture of non-straight-chain paraffin.
The monoolefine of isomerization product materials flow mild or moderate branching and phenyl compound reaction.Alkylation is carried out in comprising the alkylation part of alkylation reaction zone and alkylation disengaging zone.The present invention can use any flow process that is used for the alkylation part.The alkylation part can adopt US-A-6 basically, and mode disposes described in 187,981 B1.Can use any suitable alkylation catalyst.Alkylation catalyst comprise have BEA, MOR, MTW and the zeolite structured zeolite of NES.Described zeolite comprises mordenite, ZSM-4, ZSM-12, ZSM-20, offretite, sarcolite, β, NU-87 and gottardiite.
It is believed that alkylation conditions produces the monoolefine of isomerization product materials flow mild or moderate branching or the minimum skeletal isomerization of any other alkene and any paraffinic hydrocarbons.The minimum skeletal isomerization meaning is preferably to be less than 15mol%, and has carried out skeletal isomerization more preferably less than alkene, aliphatic alkyl chain and any reaction intermediate of 10mol%.Therefore, alkylation preferably under the situation of the skeletal isomerization of the monoolefine that does not have slight branching basically, take place and the monoolefine of slight branching in the number of primary carbon atom identical with the primary carbon atom number of each phenyl alkanes molecule.Any extra methyl branch will increase the interior primary carbon atom of phenyl alkanes product of the primary carbon atom in the monoolefine that derives from slight branching a little on the aliphatic alkyl chain of phenyl alkanes product.Finally, although the formation of 1-phenyl alkanes is unconspicuous under alkylation conditions, its generation will reduce the number of primary carbon atom in the phenyl alkanes product a little.
Phenyl compound has been produced (m with the alkylation of the monoolefine of slight branching
i-alkyl
i)
i-n-phenyl alkanes, wherein each phenyl alkanes molecule aliphatic alkyl has two, three or four primary carbon atoms.Each phenyl alkanes molecule aliphatic alkyl can have three primary carbon atoms, more preferably at two end of the chains methyl is arranged all.In this embodiment, monomethyl-phenyl alkanes has been produced in alkylation.But, all (m that produced
i-alkyl
i)
iEach phenyl alkanes molecule of-n-phenyl alkanes needn't all have the primary carbon atom of similar number.0mol%-75mol%, the and (m that produced of preferred 0mol%-40mol%
i-alkyl
i)
iEach phenyl alkanes molecule of-n-phenyl alkanes can have 2 primary carbon atoms.(the m that many and preferred as far as possible 25mol%-100mol% is produced
i-alkyl
i)
iEach phenyl alkanes molecule of-n-phenyl alkanes can have 3 primary carbon atoms.In one embodiment, (the m that 0mol%-40mol% produced
i-alkyl i) the i-n-phenyl alkanes can have 4 primary carbon atoms.Therefore, preferred (m-methyl)-n-phenyl alkanes and this paper that only has 1 methyl branch is called monomethyl-phenyl alkanes with it.Each product phenyl alkanes molecule primary, the number of the second month in a season and tertiary carbon atom can (DEPT) measure by high resolving power multipulse nucleus magnetic resonance (NMR) spectrum editor with by the undistorted enhancing (distortionless enhancement) of polarization transfer (polarization transfer), as by Bruker Instruments, Inc., Manning Park, Billerica, Massachusetts is described in the instrument specification sheets that is entitled as " High ResolutionMultipulse NMR Spectrum Editing and DEPT " of USA distribution.
Used two kinds of slightly different analyses and method of calculation to measure the selectivity parameter of alkylation in the prior art to 2-phenyl alkanes and inside season phenyl alkanes.US-A-6,111,158 and US-A-6,187,981 use the slightly different optionally method that produces.By US-A-6, after this selectivity that 111,158 method is measured is called the simplification selectivity, and by US-A-6, selectivity this paper that 187,981 method is measured is called selectivity (that is, not having modifier " simplification ").The 2-phenyl alkanes selectivity that the alkylation of the monoolefine of phenyl compound and slight branching has is 40-100, and is preferably 60-100 in another embodiment; And the phenyl alkanes selectivity is for being less than 10 inner season in one embodiment, and preferably is less than 5.
Season, phenyl alkanes can form by making the phenyl compound and the monoolefine alkylation of the slight branching with at least one tertiary carbon atom.According to the position of quaternary carbon atom with respect to the end of aliphatic alkyl chain, the inner or terminal quat of season phenyl alkanes.
Top liquid stream to the small part paraffin column in the alkylation disengaging zone is recycled to the dehydrogenation part.The recycling part of top liquid stream can be the top liquid stream of aliquot portion.This method can make any diolefine selective hydrogenation that exists in the dehydrogenation product materials flow.
The top liquid stream of some paraffin column also can be recycled to the isomerization part, because the top liquid stream of paraffin column may contain monoolefine.But the concentration of monoolefine is less than 0.3 weight % usually in the top liquid stream of paraffin column.
This method alternative is removed any aromatic hydrocarbons by product that exists in the dehydrogenation product materials flow.The aromatic hydrocarbons by product can optionally be removed from isomerization product materials flow, dehydrogenation product materials flow, the top liquid stream that is recycled to dehydrogenation paraffin column partly or selectivity diene hydrogenation product materials flow (if any).
In one embodiment, this method has been produced the MAB composition that comprises the phenyl alkanes with a phenyl and an aliphatic alkyl, and wherein phenyl alkanes has:
(i) weight in average of the aliphatic alkyl of phenyl alkanes is at C
10Aliphatic alkyl and C
13Between the weight of aliphatic alkyl;
(ii) the phenyl content that is connected to the phenyl alkanes of the 2-of aliphatic alkyl and/or 3-position is higher than 55 weight % of phenyl alkanes; With
(iii) be higher than 55 weight % of phenyl alkanes and be less than or when equaling 85 weight %, the average branching level of the aliphatic alkyl of phenyl alkanes is 0.25-1.4 alkyl of each phenyl alkanes molecule when the content summation of 2-phenyl alkanes and 3-phenyl alkanes; Or when the concentration summation of 2-phenyl alkanes and 3-phenyl alkanes was higher than 85 weight % of phenyl alkanes, the average branching level of the aliphatic alkyl of phenyl alkanes was 0.4-2.0 alkyl of each phenyl alkanes molecule; With
(iv) wherein the aliphatic alkyl of phenyl alkanes mainly comprises the aliphatic alkyl of linear aliphatic alkyl, single branching or the aliphatic alkyl of two branching, and wherein if any, alkyl branches on the aliphatic alkyl chain of aliphatic alkyl mainly comprises small-substituent, for example methyl branch, ethyl branch or propyl group side chain, and wherein if any, alkyl branches is connected to any position on the aliphatic alkyl chain of aliphatic alkyl, condition be the phenyl alkanes that has at least one quaternary carbon atom on the aliphatic alkyl constitute phenyl alkanes be less than 20%.
A method of producing above-mentioned MAB composition comprises at first makes paraffin dehydrogenation to produce corresponding monoolefine.This method comprises making to have weight in average at C
10Paraffinic hydrocarbons and C
13Monoolefine isomerization between the weight of paraffinic hydrocarbons is to produce the isomerization monoolefine of average branching level for each olefin hydrocarbon molecules 0.25-1.4 or 0.4-2.0 alkyl branches.These isomerization monoolefines mainly comprise the monoolefine of straight chain mono-olefins, single branching or the monoolefine of two branching, and if any, alkyl branches on the aliphatic alkyl chain of isomerization monoolefine mainly comprises small-substituent, for example methyl branch, ethyl branch or propyl group side chain.The alkyl branches of isomerization monoolefine can be connected to any position on the aliphatic alkyl chain of alkene, and wherein the desired characteristic according to the phenyl alkanes that finally obtains has some qualification:.The isomerization monoolefine makes the phenyl compound alkylation to produce phenyl alkanes.Resulting phenyl alkanes has following feature: the phenyl alkanes that phenyl is connected to the 2-of aliphatic alkyl and/or 3-position constitutes the 55 weight % that are higher than of phenyl alkanes, and the phenyl alkanes that has at least one quaternary carbon atom on the aliphatic alkyl constitute phenyl alkanes be less than 20%.
The sulfonation of the phenyl alkanes of producing by method of the present invention and the neutralization of sulfonated products can pass through US-A-6, the realization of method described in 187,981.
In others of the present invention, the present invention is MAB composition and the MABS composition of producing by method disclosed herein.The MAB composition of producing by method of the present invention can comprise lubricant, and the MABS composition of producing by method of the present invention can comprise lubricant additive.
Accompanying drawing is represented the design of dehydrogenation-isomerization of the present invention-alkylation entire flow.Accompanying drawing represents to comprise C
10-C
13The paraffinic feedstock of n-paraffin enters technology by pipeline 10.Mobile comprises C in paraffinic feedstock and the pipeline 46
10-C
13The paraffinic hydrocarbons recycle stream of n-paraffin mixes mobile parallel feeding materials flow in the formation pipeline 12, and described parallel feeding materials flow enters dehydrogenation part 14 so that paraffin dehydrogenation is an alkene.Pipeline 16 ejects the hydrogen from technology.Dehydrogenation product materials flow in the pipeline 18 contains C
10-C
13N-paraffin, C
10-C
13Positive monoolefine, C
10-C
13Positive diolefine and aromatic hydrocarbons by product.Selective hydrogenation part 20 receives additional hydrogen so that the diolefine selective hydrogenation in the dehydrogenation product materials flow is a monoolefine by pipeline 22, thereby removes C
10-C
13Positive diolefine.The materials flow of selective hydrogenation product flows to isomerisation of olefin part 26 by pipeline 24, and described isomerisation of olefin partly makes the original olefin isomerization turn to the monoolefine of slight branching.Isomerization product materials flow in the pipeline 28 contains C
10-C
13Monoolefine, the C of slight branching
10-C
13N-paraffin and aromatic hydrocarbons by product.Aromatic hydrocarbons is removed part 30 and is removed the aromatic hydrocarbons by product and they are discharged from technology through pipeline 32.Aromatic hydrocarbons is removed the portion of product materials flow and is flowed to alkylation part 52 through pipeline 34, and described alkylation partly comprises alkylation reaction zone 36 and alkylation disengaging zone 40.Aromatic hydrocarbons is removed the phenyl recycle stream that portion of product materials flow and pipeline 44 contain benzene be fed to alkylation reaction zone 36, wherein C
10-C
13The monoolefine of slight branching makes benzene alkylation to produce MAB.The materials flow of alkylation reaction zone effluent contains benzene, C
10-C
13N-paraffin, MAB and heavy alkyl benzene be the by product polyalkylbenzene for example.Described effluent materials flow flows to alkylation disengaging zone 40 through pipeline 38.The phenyl charging that comprises benzene flows to disengaging zone 40 through pipeline 42.Mobile phenyl recycle stream in the pipeline 44 has been reclaimed in alkylation disengaging zone 40, the paraffinic hydrocarbons recycle stream in the pipeline 46, the heavy alkyl benzene of discharging from technology through pipeline 50 and the product materials flow that comprises MAB of carrying through pipeline 48.
This paper for all of family of elements with reference to all and the periodic table of elements, " CRC Handbook ofChemistry and Physics ", CRC press, Boca Raton, Florida, the 80th edition, 1999-2000 is relevant.
Embodiment 1
100cc is comprised catalyst sample that 50 weight % are combined with the MgAPSO-31 of gamma-alumina, and to place internal diameter be in the reactor tube of 2.22cm (7/8 inch).Making the charging of the mixture that comprises the 1-dodecylene is 5hr at the liquid hourly space velocity degree
-1Under pass through catalyzer.Catalyst temperature is initially set in 250 ℃ (482 ℉), and then it is regulated to keep required normal olefine transformation efficiency.
Shunting/Hewlett Packard (HP) the gas-chromatography HP5890 of split stream injector does not analyze and uses flame ionization detector (FID) to product by being equipped with.Gas-chromatography is equipped with the hydrogenation unit tubular stinger in syringe.Post is that internal diameter is 50 meters Hewlett Packard HPPONA posts of 0.2mm.Use red light barrier film (septa) of 11mm Restek and inlet liner to use HP O shape ring.The gas-chromatography parameter comprises: the hydrogen carrier gas; 138kPa (g) (20psi (g)) column head pressure; 1mm/min post stream; The 250ml/min multiple exhaust; The 4ml/min barrier film dashes and sweeps; 0.2 microlitre volume injected; 175 ℃ of (367 ℉) injector temperature; 275 ℃ of (527 ℉) detector temperatures and be included in 50 ℃ (122 ℉) and stopped 5 minutes down are with the 3 ℃/10min (alternating temperature to 175 ℃ (347 ℉) of 5 ℉/min) and at the 10 ℃/min (program oven temperature of alternating temperature to 270 ℃ (518 ℉) of 18 ℉/min).Sample is ready for injection by taking by weighing the 4-5mg sample to 2ml gas-chromatography self-actuated sampler bottle.Hydrogenation unit passes through the formulations prepared from solutions of preparation 20g nickelous nitrate hexahydrate and 40ml methyl alcohol with catalyzer.Nickel nitrate solution slowly pours on the interior 20g " Chromosorb P " of furnace pot, and described " Chromosorb P " is the calcined diatomite of being made by broken refractory brick.Mixture in the furnace pot is heated to 65 ℃ (149 ℉) so that methyl alcohol evaporates until the mixture drying on hot-plate under constant agitation.The 3g mixture placed in the hydrogenation unit tubular stinger and fixing at two ends to be fixed in its position with glass wool.For deactivated catalyst, make the hydrogen carrier gas under 60ml/min, rise to 350 ℃ (662 ℉) by catalyzer and with temperature, and under these conditions with catalyst treatment 3 hours.The required standard model of aforesaid method is n-decane, n-undecane, n-dodecane, n-tridecane and n-tetradecane.The relative position of monomethyl isomer provides in the article of aforementioned H.Schultz etc.
Product is summarised as 5 following classification, and each classification summary is as shown in bracket: carbon number is 11 or lower light product [C
11-], the alkene [two] and the carbon number of alkene [list], dimethyl and the ethyl branching of normal olefine [straight chain], monomethyl branching be C
13Or higher heavy product [C
13+].And be calculated as follows performance metric:
Transformation efficiency=100* (1-([straight chain]
Product/ [straight chain]
Charging))
Monomethyl=100* ([list]/([list]+[two]))
Light product=100* ([C
11-]/([C
11-]+[straight chain]+[list]+[two]+[C
13+]))
Heavy product=100* ([C
13+]/([C
11-]+[straight chain]+[list]+[two]+[C
13+]))
The results are shown in table 1:
Table 1: result
| Transformation efficiency | Monomethyl | Light product | Heavy product |
| 69.9 | 86.8 | 0.64 | 3.53 |
Embodiment 2
Repeat embodiment 1, but charging comprises C
11, C
12And C
13The mixture of normal olefine.Charging comprises 28.7mol%C
11, 39.6mol%C
12And 31.7mol%C
13Product comprises the alkene of monomethyl branching.The alkene of monomethyl branching is distributed as 30.9mol%C in the product
11, 42.4mol%C
12And 26.7mol%C
13This embodiment shows that under the situation that does not have recirculation the carbon atom that the carbon number distribution of the olefin product of monomethyl branching is different from charging distributes.
Embodiment 3
This technology is operated as shown in the drawing, but does not have mobile paraffinic hydrocarbons recycle stream in the pipeline 46.Paraffinic feedstock enters this technology and reclaim MAB in pipeline 48 by pipeline 10, and this technology is operated under steady state conditions.The mobile materials flow has the feed composition among the embodiment 2 in the pipeline 24, and the mobile materials flow has product materials flow among the embodiment 2 in the pipeline 28.Start flowing of paraffinic hydrocarbons recycle stream in the pipeline 46 then.In case reconstruction steady state conditions, the carbon number of acquisition when under no paraffinic hydrocarbons recycle stream, operating that the distribution of the carbonatoms of the aliphatic alkyl of MAB product deflection is lower than this technology.
Embodiment 4
This technology is operated as shown in drawings.Paraffinic feedstock enters technology by pipeline 10 and reclaim MAB in pipeline 48, and this technology is operated under steady state conditions.The mobile materials flow has the composition shown in the table 1 in the pipeline 28.
Embodiment 5
Make the isomerization of 1-dodecylene raw material to produce the isomerization product materials flow, described isomerization product materials flow comprises monomethyl C
12The mixture of alkene and have shown in the table 2 is formed.
Table 2: the composition of isomerization product materials flow
| The alkene component | Content (weight %) |
| Light product 1 | 0.64 |
| Normal olefine 2 | 30.11 |
| 6-methyl undecylene | 7.66 |
| 5-methyl undecylene | 15.33 |
| 4-methyl undecylene | 11.82 |
| 3-methyl undecylene | 12.95 |
| 2-methyl undecylene | 8.87 |
| Other alkyl alkene 3 | 9.05 |
| Heavy product 4 | 3.53 |
| Amount to | 99.96 |
1Light product comprises having the alkene that is less than 12 carbon atoms.
2Normal olefine comprises C
12Normal olefine.
3Other alkyl alkene comprises dimethyl, trimethylammonium and other C
12Alkene.
4Heavy product comprises C
12Olefin dimers and trimer.
The isomerization product materials flow mixes the parallel feeding that comprises 93.3 weight % benzene and 6.7 weight % isomerization product materials flows with production with benzene, its mol ratio that is equivalent to benzene/alkene is 30:1.With internal diameter is the barrel reactor of 0.875 inch (22.2mm) 75cc (53.0g) US-A-6 that packs into, the extrudate for preparing among 111,158 the embodiment.
Reactor is sent in parallel feeding, and be 2.0hr at LHSV
-1, stagnation pressure be 500psi (g) (3447kPa (g)) with reactor inlet temperature is that 125 ℃ (257 ℉) contact extrudate down.Under these conditions, reactor moved rapidly in 24 hours time, and collected first product liquid then in the ensuing 6 hours time.
After collecting first product liquid 6 hours, and be 2.0hr at LHSV in parallel feeding
-1With stagnation pressure is to flow under the situation of reactor under the 500psi (g) (3447kPa (g)), makes reactor inlet temperature rise to 150 (302 ℉) from 125 ℃ (257 ℉).By parallel feeding being delivered to reactor and being 2.0hr at LHSV
-1, stagnation pressure be 500psi (g) (3447kPa (g)) with reactor inlet temperature is that 150 ℃ (302 ℉) contacts extrudate down, make reactor in 12 hours time according to the system operation that installs.Under these conditions, in the ensuing 6 hours time, collect second product liquid.The result of second product liquid is as shown in table 3.
After collection second product liquid 6 hours, the mobile LHSV of remaining on that makes parallel feeding is 2.0hr
-1With stagnation pressure be under the 500psi (g) (3447kPa (g)).Under these conditions, make reactor inlet temperature rise to 175 (347 ℉) from 150 ℃ (302 ℉).By parallel feeding being delivered to reactor and being 2.0hr at LHSV
-1, stagnation pressure be 500psi (g) (3447kPa (g)) with reactor inlet temperature is that 175 ℃ (347 ℉) contacts extrudate down, reactor in 12 hours time according to the system operation that installs.Under these conditions, in the ensuing 6 hours time, collect the 3rd product liquid.The 3rd product liquid adopts aforementioned manner to pass through
13C NMR analyzes.The inside season phenyl alkanes selectivity of the 2-phenyl alkanes selectivity of the simplification of the 3rd product liquid and simplification is as shown in table 3.Final season, the phenyl alkanes selectivity used US-A-6, and the analysis and the method for calculation of being instructed in 187,981 are measured.
Table 3: liquid product analyses
| Reactor inlet temperature ℃ (℉) | The 2-phenyl alkanes selectivity of simplifying | The inside season phenyl alkanes selectivity of simplifying |
| 150(302) | 66.4 | 4.6 |
| 175(347) | 77.7 | 2.9 |
Therefore, the 2-phenyl alkanes selectivity that has of the alkylation among the embodiment be 40-100 and inner season the phenyl alkanes selectivity be less than 10.Although this embodiment does not utilize paraffinic hydrocarbons recirculation, it is believed that if paraffinic hydrocarbons recirculation used according to the invention, then 2-phenyl alkanes selectivity also will for 40-100 and inner season the phenyl alkanes selectivity will be less than 10.
Claims (20)
1, a kind of method of producing phenyl alkanes, this method comprises the steps:
A) make in the part of the dehydrogenation under operating in the dehydrogenation condition that is enough to make paraffin dehydrogenation and comprise C
8-C
28The charging dehydrogenation of paraffinic hydrocarbons, and from the partially recycled dehydrogenation product materials flow that comprises monoolefine and paraffinic hydrocarbons of dehydrogenation;
B) materials flow of near small part dehydrogenation product is delivered in the isomerization part that operates under the isomerisation conditions that is enough to make isomerisation of olefin, and from the partially recycled isomerization product materials flow that comprises monoolefine and paraffinic hydrocarbons of isomerization, wherein the monoolefine in the isomerization product materials flow has 8-28 carbon atom, and wherein has 3 or 4 primary carbon atoms and do not have quaternary carbon atom to the small part monoolefine in the dehydrogenation product materials flow;
C) deliver to the alkylation part with phenyl compound with to the isomerization product materials flow that small part comprises monoolefine, be enough to adopt monoolefine making under the alkylating alkylation conditions of phenyl compound operation alkylation part in the presence of the alkylation catalyst to form phenyl alkanes, described phenyl alkanes comprises such molecule, be that it has a phenyl moiety and an aliphatic alkyl part, it comprises 8-28 carbon atom; Wherein except any quaternary carbon atom of the carbon atom keyed jointing by C-C and phenyl moiety, what form in the alkylation part has 2,3 or 4 primary carbon atoms and does not have quaternary carbon atom to the small part phenyl alkanes; And wherein alkylation is 40-100 to the selectivity of 2-phenyl alkanes, and the selectivity of inside season phenyl alkanes is less than 10;
D) from the partially recycled recycle stream that comprises the alkylate materials flow of phenyl alkanes and comprise paraffinic hydrocarbons of alkylation; With
E) near small part recycle stream is delivered to the dehydrogenation part.
2, the method for claim 1, it is further characterized in that to materials flow of small part dehydrogenation product and to the materials flow of small part isomerization product at least one and comprises the monoolefine of slight branching.
3, the method for claim 2, wherein the concentration to the monoolefine of the slight branching of small part isomerization product materials flow is higher than to the 25mol% of small part isomerization product materials flow
4, claim 2 or 3 method, it is further characterized in that and comprises straight chain mono-olefins to the small part monoolefine to materials flow of small part isomerization product and to the materials flow of small part dehydrogenation product at least one.
5, the method for claim 4 wherein is less than or equals 75mol% to the concentration of the straight chain mono-olefins of small part isomerization product materials flow.
6, claim 2 or 3 method, it is further characterized in that to have at least one quaternary carbon atom to the small part monoolefine to materials flow of small part dehydrogenation product and to the materials flow of small part isomerization product at least one.
7, the method for claim 4, it is further characterized in that to have at least one quaternary carbon atom to the small part monoolefine to materials flow of small part dehydrogenation product and to the materials flow of small part isomerization product at least one.
8, the method for claim 5, it is further characterized in that to have at least one quaternary carbon atom to the small part monoolefine to materials flow of small part dehydrogenation product and to the materials flow of small part isomerization product at least one.
9, each method among the claim 6-8, wherein the concentration to the alkene that contains at least one quaternary carbon atom of small part isomerization product materials flow is less than 10mol%.
10, the process of claim 1 wherein that the weight in average of aliphatic alkyl of phenyl alkanes is at C
10Aliphatic alkyl and C
13Between the weight of aliphatic alkyl; The content that phenyl is connected to the phenyl alkanes of the 2-of aliphatic alkyl and/or 3-position is higher than 55 weight % of phenyl alkanes; When the summation of the content of 2-phenyl alkanes and 3-phenyl alkanes is higher than 55 weight % of phenyl alkanes and is less than or when equaling 85 weight %, the average branching level of the aliphatic alkyl of phenyl alkanes is 0.25-1.4 alkyl of each phenyl alkanes molecule, or when the concentration summation of 2-phenyl alkanes and 3-phenyl alkanes was higher than 85 weight % of phenyl alkanes, the average branching level of the aliphatic alkyl of phenyl alkanes was 0.4-2.0 alkyl of each phenyl alkanes molecule; The aliphatic alkyl of phenyl alkanes comprises the aliphatic alkyl of linear aliphatic alkyl, single branching or the aliphatic alkyl of two branching; If present, the alkyl branches on the aliphatic alkyl chain of aliphatic alkyl comprises methyl branch, ethyl branch or propyl group side chain; And if present, alkyl branches is connected on any position of aliphatic alkyl chain of aliphatic alkyl, condition be the aliphatic alkyl that has at least one quaternary carbon atom on the phenylalkyl constitute phenyl alkanes be less than 20%.
11, the method for claim 1, it is further characterized in that dehydrogenation partly comprises dehydrogenation catalyst, described dehydrogenation catalyst comprises at least a VIII (IUPAC 8-10) family's metal and is dispersed in the outer interior promoter metal of the inorganic oxide that is attached on the refractory inorganic oxide, and described catalyzer comprises kernel and further is dispersed with the dehydrogenation catalyst of properties-correcting agent metal thereon.
12, the method for claim 1, it is further characterized in that isomerization partly comprises isomerization catalyst, described isomerization catalyst comprises the solid support material that is selected from ferrierite, SAPO-11 and MgAPSO-31.
13, the method for claim 1, it is further characterized in that isomerization partly comprises isomerization catalyst, and described isomerization catalyst comprises VIII (IUPAC 8-10) family's metal and isomerization part operation, and to be higher than 0.01:1 and temperature in the mol ratio that comprises hydrogen/hydrocarbon be under 50-400 ℃ the isomerisation conditions.
14, the method for claim 1, it is further characterized in that alkylation catalyst comprises the zeolite with the zeolite structure type that is selected from BEA, MOR, MTW and NES.
15, the process of claim 1 wherein that monoolefine comprises monomethyl alkene and phenyl alkanes comprises monomethyl-phenyl alkanes.
16, the method for claim 1, it is further characterized in that to the monoolefine concentration of small part recycle stream and is less than 0.3 weight %.
17, a kind of modified alkylbenzene composition, wherein modified alkylbenzene is by each method production among the claim 1-16.
18, according to the modified alkylbenzene composition of claim 17, wherein the modified alkylbenzene composition comprises lubricant or lubricant additive.
19, each method among the claim 1-16, it is further characterized in that under the sulfonation condition of the sulfonated products materials flow that is enough to make phenyl alkanes sulfonation and production comprise phenyl alkanes sulfonic acid partially alkylated at least product materials flow is contacted with sulphonating agent, and is being enough under the neutrality condition that makes the neutralization of phenyl alkanes sulfonic acid and produce the neutralized reaction product materials flow that comprises phenyl alkanes sulfonate partly sulfonated at least product materials flow to be contacted with neutralizing agent.
20, a kind of modified alkylbenzene sulfonates composition, wherein modified alkylbenzene sulfonates is by the method production of claim 19.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2003/040854 WO2005068405A1 (en) | 2003-12-22 | 2003-12-22 | Process for producing phenyl-alkanes using olefin isomerization and paraffin recycle |
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|---|---|
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| CN100497272C true CN100497272C (en) | 2009-06-10 |
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|---|---|
| CN (1) | CN100497272C (en) |
| AU (1) | AU2003297448A1 (en) |
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| US10308896B2 (en) * | 2015-08-10 | 2019-06-04 | The Procter & Gamble Company | Methods for producing alkylbenzenes, paraffins, olefins and oxo alcohols from waste plastic feedstocks |
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| US6187981B1 (en) * | 1999-07-19 | 2001-02-13 | Uop Llc | Process for producing arylalkanes and arylalkane sulfonates, compositions produced therefrom, and uses thereof |
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