CN105503495B - A kind of method for reducing linear alkylbenzene (LAB) bromine index - Google Patents
A kind of method for reducing linear alkylbenzene (LAB) bromine index Download PDFInfo
- Publication number
- CN105503495B CN105503495B CN201511029447.2A CN201511029447A CN105503495B CN 105503495 B CN105503495 B CN 105503495B CN 201511029447 A CN201511029447 A CN 201511029447A CN 105503495 B CN105503495 B CN 105503495B
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- lab
- sio
- linear alkylbenzene
- 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.)
- Active
Links
- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 61
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 43
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000003054 catalyst Substances 0.000 claims abstract description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 150000001336 alkenes Chemical class 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 39
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 39
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 230000029936 alkylation Effects 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 24
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims description 98
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 86
- 238000007598 dipping method Methods 0.000 claims description 70
- 238000005984 hydrogenation reaction Methods 0.000 claims description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 62
- 238000010792 warming Methods 0.000 claims description 49
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 42
- 235000014121 butter Nutrition 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 38
- 229910052697 platinum Inorganic materials 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 22
- 229910002846 Pt–Sn Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000012018 catalyst precursor Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 230000002779 inactivation Effects 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009418 renovation Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 claims 1
- CPWPJLJWUXOOAB-UHFFFAOYSA-N benzene;bromine Chemical compound [Br].C1=CC=CC=C1 CPWPJLJWUXOOAB-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 239000000243 solution Substances 0.000 description 108
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- -1 alkane alkene hydrocarbon Chemical class 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- 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
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method for reducing linear alkylbenzene (LAB) bromine index, described method is：In 60~350 DEG C of temperature, 0.3~10.0MPa of pressure, mass space velocity 0.2~10.0 hour‑1, hydrogen to oil volume ratio 300:1~8000:Under conditions of 1, hydrogenating materials and hydrogen are mixed, with Pt Sn/SiO2Loaded catalyst haptoreaction, makes alkene saturation, and then reduces linear alkylbenzene (LAB) bromine index, improves product quality；The hydrogenating materials are benzene and C10~C14The linear alkylbenzene (LAB) that linear alkene alkylation mixture is obtained through separated, or benzene and C10~C14Linear alkene alkylation mixture；Present invention process flow is simple, and catalyst activity stability is good, and the device stable operation time is long, can avoid reactor reaction and regeneration frequent switching operation, and linear alkylbenzene (LAB) loss is few, and catalyst is renewable, and a large amount of dead catalyst can be avoided to post-process, and effect on environment is small.
Description
(1) technical field
The present invention relates to a kind of method for reducing linear alkylbenzene (LAB) bromine index, especially one kind uses Pt-Sn/SiO2Catalysis
Agent carries out catalytic hydrogenation reaction, the method for reducing linear alkylbenzene (LAB) bromine index.
(2) background technology
Benzene and C10~C14The linear alkylbenzene (LAB) of linear alkene alkylation production is the primary raw material of synthetic detergent.At present
Dehydrogenation-HF alkylation process the technologies of Uop Inc. are industrially generally used, to produce linear alkylbenzene (LAB).Due to HF alkyl chemical industry
Skill has that equipment corrosion is serious, it is substantial amounts of liquid and waste slag produced to produce, and the problems such as potential production safety, has carried out both at home and abroad without corruption
Corrosion solid acid catalyst and the research of environment-friendly alkylation process, the fixed bed that Uop Inc. and Petresa companies develop jointly
Solid acid catalysis Detal alkylation process realizes industrial applications, the technique alkylated reaction and catalyst detergent regeneration 24h
Handover operation.
Producing the technical process of linear alkylbenzene (LAB) is, C10~C14Linear paraffin passes through dehydrogenation, and then chosen property hydrogenation is de-
Except alkadienes, straight chain alkane alkene hydrocarbon mixture is obtained；Liquid HF catalysis or solid acid through the alkene in straight chain alkane alkene hydrocarbon mixture and benzene
Catalytic alkylation reaction, and separated, obtain linear alkyl benzene product.Due to containing in raw material for alkylation alkane alkene hydrocarbon mixture
A small amount of alkadienes, itself and benzene reaction generate phenyl alkene, and are difficult to further conversion completely, make alkylate straight chain alkane
Contain a small amount of unsaturated hydrocarbons in base benzene.In addition, during alkylation mixture separated, being influenceed by thermal cracking, make
Separated straight chained alkyl benzene fraction unsaturated hydrocarbons content increased.These cause linear alkylbenzene (LAB) bromine index to increase.Straight chain
Alkylbenzene bromine index indicates the color of alkylbenzene presence of unsaturates, influence alkylbenzene quality stability and alkylbenzenesulfonate
Pool.Alkylbenzene bromine index is generally industrially reduced using clay treatment process, its spent bleaching clay needs landfill disposal, pollutes environment,
And linear alkylbenzene (LAB) loss is larger.Linear alkylbenzene (LAB) bromine index is reduced with catalytic hydrogenation method, improves product quality, is effective
Developing direction.
Metal platinum can activate hydrogen atom, catalytic hydrogenation reaction.Tin is added on platinum as auxiliary agent, Pt/Sn bimetallics are made
Catalyst, the catalytic selectivity and stability compared with monometallic Pt catalyst be more preferable.There is electronic effect to Pt components in Sn auxiliary agents
Acted on two aspects of geometric effect.In terms of electronic effect, the electro transfer between Sn and Pt changes Pt and ADSORPTION STATE
Bond strength between hydrocarbon.In terms of geometric effect, Pt surface segmentations into smaller cluster, are improved Pt by Sn
Decentralization.By the load of Pt/Sn bimetallics on the porous material, loaded catalyst is prepared, is increasing specific surface area and catalysis
The effective way of activity.
Loaded catalyst is prepared using incipient impregnation method, catalytic active component can be effectively utilized.In dipping
Source metal, by adding complexing agent into dipping solution, improves scattered journey of the source metal on carrier to during on carrier
Degree, increases metal surface area, improves the high active of hydrogenation catalysis of loaded catalyst.In addition, in source metal dipping process, utilizing
The peptizaiton of ultrasonic wave, improves degree of scatter of the source metal on carrier, improves the catalytic activity of loaded catalyst.Utilize
The good hydrogenation loaded catalyst of these method processabilities, the catalytic hydrogenation method of linear alkylbenzene (LAB) bromine index is reduced to research
It is significant.
(3) content of the invention
It is an object of the present invention to provide a kind of method for reducing linear alkylbenzene (LAB) bromine index, i.e., using Pt-Sn/SiO2Catalyst
Catalytic hydrogenation reaction is carried out, the method for reducing linear alkylbenzene (LAB) bromine index solves clay-filtered spent bleaching clay landfill disposal institute
Caused environmental pollution, and linear alkylbenzene (LAB) loss it is larger the problem of.
The technical solution adopted by the present invention is：
The present invention provides a kind of method for reducing linear alkylbenzene (LAB) bromine index, and described method is：In temperature 60~350
DEG C, 0.3~10.0MPa of pressure, mass space velocity 0.2~10.0 hour-1, hydrogen to oil volume ratio (i.e. hydrogen and hydrogenating materials volume ratio)
300:1~8000:Under conditions of 1, hydrogenating materials and hydrogen are mixed, with Pt-Sn/SiO2Loaded catalyst haptoreaction,
Make alkene saturation, and then reduce linear alkylbenzene (LAB) bromine index, improve product quality；Regenerated after catalyst inactivation through hydrogenation, circulation
Utilize；
The hydrogenating materials are one of following：(1) benzene and C10~C14Linear alkene alkylation mixture is obtained through separated
The linear alkylbenzene (LAB) arrived；(2) benzene and C10~C14Linear alkene alkylation mixture；
Described Pt-Sn/SiO2Loaded catalyst is with SiO2For carrier, using Pt and Sn as active component, Pt mass loadings
It is 0.5 to measure as the ratio between 0.2~5.0%, Pt and Sn mass loading amounts:1~2:1.
Further, preferably described Pt mass loadings amount is 0.5~3.0%, Pt and the ratio between Sn mass loading amounts are 1:1~2:
1。
Further, preferably described hydrogenating materials are benzene and C10~C14Linear alkene alkylation mixture is obtained through separated
The linear alkylbenzene (LAB) arrived, its bromine index is 20~800mgBr/100g, and preferably bromine index is 30~500mgBr/100g.
Further, preferably described hydrogenating materials are benzene and C10~C14Linear alkene alkylation mixture, its benzene and straight chain alkane
Base benzene mass fraction is respectively 15~60%, 5~15%, and remaining is C10~C14Linear paraffin, the bromine index of alkylation mixture
For 20~800mgBr/100g, preferred alkylation mixture bromine index is 30~500mgBr/100g, its benzene and straight chain alkane
Base benzene mass fraction is respectively 25~55%, 6~12%, and remaining is C10~C14Linear paraffin.
The present invention most preferably hydrogenation reaction raw material is one of following：(1) benzene and C10~C14Linear alkene alkylation mixture
Through the isolated linear alkylbenzene (LAB) of vacuum distillation, its bromine index is 227.63mgBr/100g；(2) benzene and C10~C14Straight chain alkene
Alkylating hydrocarbons mixture is through the isolated linear alkylbenzene (LAB) of vacuum distillation, and its bromine index is 28.18mgBr/100g；(3) benzene with
C10~C14Linear alkene alkylation mixture is through the isolated linear alkylbenzene (LAB) of vacuum distillation, its bromine index
493.52mgBr/100g；(4) benzene and C10~C14Linear alkene alkylation mixture, its benzene, linear alkylbenzene (LAB), C10~C14Straight chain
The mass fraction of alkane is respectively 52.48%, 6.65%, 40.87%, and bromine index is 315.18mgBr/100g；(5) benzene and C10
~C14Linear alkene alkylation mixture, its benzene, linear alkylbenzene (LAB), C10~C14The mass fraction of linear paraffin is respectively
15.71%th, 11.87%, 72.42%, bromine index is 516.25mgBr/100g；(6) it is benzene and C10~C14Linear alkene alkyl
Change mixture, its benzene, linear alkylbenzene (LAB), C10~C14The mass fraction of linear paraffin is respectively 57.46%, 5.99%,
36.55%, bromine index is 37.67mgBr/100g.
Further, preferably described hydrogenation conditions are 80~300 DEG C of temperature, 0.5~5.0MPa of pressure, and feedstock quality is empty
Speed 0.5~5.0 hour-1, hydrogen to oil volume ratio 600:1~6000:1, most preferably described hydrogenation conditions are temperature 100~300
DEG C, 1.0~4.0MPa of pressure, feedstock quality air speed 0.5~2.0 hour-1, hydrogen to oil volume ratio 1000:1~3000:1.
Pt-Sn/SiO of the present invention2Loaded catalyst is prepared using incipient impregnation method：Chloroplatinic acid is dissolved in
HCl mass fractions for 2%~20% aqueous hydrochloric acid solution (preferably 5%~15%) in, obtain platinum acid chloride solution；By butter of tin
It is dissolved in the aqueous hydrochloric acid solution (preferably 5%~15%) that HCl mass fractions are 2%~20%, obtains butter of tin solution；In nitrogen
Under gas shielded, stirring, room temperature condition, butter of tin solution is slowly dropped in platinum acid chloride solution, dipping solution, dipping is formed
Liquor capacity is equal with the volume of catalyst carrier maximum adsorption water；Dipping solution is added dropwise while stirring into carrier, drips
2~24h is stood after finishing；Then, 2~24h (5~20h is dried at preferably 85~95 DEG C) is dried at 80~100 DEG C, with 1~10
DEG C/min rate program is warming up to 450~600 DEG C, (preferably 1~5 DEG C/min is warming up to 450~550 to 1~10h of constant temperature calcining
DEG C, 2~6h of constant temperature), obtain solid；Compare 10 in distilled water and solid volume:1~50:(preferably 20 under the conditions of 1:1~40:1),
3~8h of washing is stirred at room temperature with distilled water, is separated by filtration, repeated washing and filtering 2~10 times, then through drying 2 at 80~100 DEG C
~24h (dries 5~20h) at preferably 85~95 DEG C, 200~400 DEG C, constant temperature are warming up to 1~10 DEG C/min rate program
1~10h (preferably 1~5 DEG C/min is warming up to 250~350 DEG C, 2~6h of constant temperature) is calcined, catalyst precursors are obtained；Finally, adopt
The mode of reduction in reactor tube is taken, in 0.2~3.0MPa of pressure, 100~2000h of hydrogen volume air speed-1, with 1~5 DEG C/min
Speed be warming up to 120~250 DEG C under the conditions of reduction 1~8h (preferably 1.0~2.5MPa, 200~1000h-1, 1~3 DEG C/min
Reductase 12~5h under the conditions of being warming up to 150~250 DEG C), obtain Pt-Sn/SiO2Loaded catalyst；Chlorine in the dipping solution
Platinic acid concentration is 3.0 × 10-6~8.0 × 10-3Mol/L (preferably 8.5 × 10-6~2.2 × 10-4Mol/L), butter of tin concentration
For 3.0 × 10-6~8.0 × 10-3Mol/L (preferably 2.8 × 10-5~2.2 × 10-4Mol/L), the dipping solution volumetric usage
0.5~5.5mL/g (preferably 1.2~3.6mL/g) is calculated as with carrier quality.
Pt-Sn/SiO of the present invention2Loaded catalyst can also be prepared using complexing dipping method：Made with citric acid
For complexing agent, by chloroplatinic acid and citric acid be dissolved in aqueous hydrochloric acid solution that HCl mass fractions are 2%~20% (preferably 5%~
15%) in, citric acid is 1 with chloroplatinic acid mol ratio:1~4:1 (preferably 1:1~3:1) platinum acid chloride solution, is obtained；By four chlorinations
Tin is dissolved in the aqueous hydrochloric acid solution (preferably 5%~15%) that HCl mass fractions are 2%~20%, obtains butter of tin solution；
Under nitrogen protection, stirring, room temperature condition, butter of tin solution is slowly dropped in platinum acid chloride solution, dipping solution, leaching is formed
Stain liquor capacity is equal with the volume of catalyst carrier maximum adsorption water；Dipping solution is added dropwise while stirring into carrier, 2 are stood
~24h；Then, 2~24h (5~20h is dried at preferably 85~95 DEG C) is dried at 80~100 DEG C, with 1~10 DEG C/min's
Rate program is warming up to 450~600 DEG C, and (preferably 1~5 DEG C/min is warming up to 450~550 DEG C, constant temperature 2 to 1~10h of constant temperature calcining
~6h), obtain solid；Compare 10 in distilled water and solid volume:1~50:(preferably 20 under the conditions of 1:1~40:1) distilled water, is used
3~8h of washing is stirred at room temperature, is separated by filtration, repeated washing and filtering 2~10 times, then it is (excellent through drying 2~24h at 80~100 DEG C
Select and 5~20h dried at 85~95 DEG C), it is warming up to 200~400 DEG C with 1~10 DEG C/min rate program, constant temperature calcining 1~
10h (preferably 1~5 DEG C/min is warming up to 250~350 DEG C, 2~6h of constant temperature), obtains catalyst precursors；Finally, reaction is taken
The mode of reduction in device pipe, in 0.2~3.0MPa of pressure, 100~2000h of hydrogen volume air speed-1, with 1~5 DEG C/min speed
1~8h (preferably 1.0~2.5MPa, 200~1000h are reduced under the conditions of being warming up to 120~250 DEG C-1, 1~3 DEG C/min is warming up to
Reductase 12~5h under the conditions of 150~250 DEG C), obtain Pt-Sn/SiO2Loaded catalyst；The citric acid and chloroplatinic acid material
The ratio between amount be 1:1~4:1, chloroplatinic acid concentration is 3.0 × 10 in the dipping solution-6~8.0 × 10-3Mol/L (preferably 8.5
×10-6~2.2 × 10-4Mol/L), butter of tin concentration is 3.0 × 10-6~8.0 × 10-3Mol/L (preferably 2.8 × 10-5~
2.2×10-4Mol/L), the dipping solution volumetric usage is calculated as 0.5~5.5mL/g (preferably 1.2~3.6mL/ with carrier quality
G), citric acid concentration is 3.0 × 10-6~3.2 × 10-2Mol/L (preferably 1.0 × 10-4~5.2 × 10-4mol/L)。
Pt-Sn/SiO of the present invention2Loaded catalyst can also be prepared using ultrasonic immersing method：Chloroplatinic acid is molten
In the aqueous hydrochloric acid solution (preferably 5%~15%) that HCl mass fractions are 2%~20%, platinum acid chloride solution is obtained；By four chlorinations
Tin is dissolved in the aqueous hydrochloric acid solution (preferably 5%~15%) that HCl mass fractions are 2%~20%, obtains butter of tin solution；
Under nitrogen protection, stirring, room temperature condition, butter of tin solution is slowly dropped in platinum acid chloride solution, dipping solution, leaching is formed
Stain liquor capacity is 1~3 times of catalyst carrier maximum adsorption water volume；Dipping solution is added dropwise while stirring into carrier, plus
After complete dipping solution, ultrasonically treated 10~60min under the conditions of room temperature, supersonic frequency 40kHz, 30~100W of ultrasonic power is quiet
Put 2~24h (preferably 40~80W W 15~40min of ultrasound stand 5~8h)；Then, 2~24h is dried at 80~100 DEG C
(preferably 85~95 DEG C dry 5~20h), 450~600 DEG C are warming up to 1~10 DEG C/min rate program, and constant temperature calcining 1~
10h (preferably 1~5 DEG C/min is warming up to 450~550 DEG C, 2~6h of constant temperature), obtains solid；In distilled water and solid volume ratio
10:1~50:(preferably 20 under the conditions of 1:1~40:1) 3~8h of washing, is stirred at room temperature with distilled water, is separated by filtration, repeated washing
With filtering 2~10 times, then through at 80~100 DEG C dry 2~24h (preferably 85~95 DEG C dry 5~20h), with 1~10 DEG C/min
Rate program be warming up to 200~400 DEG C, (preferably 1~5 DEG C/min is warming up to 250~350 DEG C, constant temperature to 1~10h of constant temperature calcining
2~6h), obtain catalyst precursors；Finally, the mode of reduction in reactor tube is taken, in 0.2~3.0MPa of pressure, hydrogen
100~2000h of volume space velocity-1, be warming up to 120~250 DEG C with 1~5 DEG C/min speed under the conditions of reduce 1~8h (preferably 1.0
~2.5MPa, 200~1000h-1, 1~3 DEG C/min be warming up to 150~250 DEG C under the conditions of reductase 12~5h), obtain Pt-Sn/
SiO2Loaded catalyst；Chloroplatinic acid concentration is 3.0 × 10 in the dipping solution-6~8.0 × 10-3Mol/L (preferably 8.5 ×
10-6~2.2 × 10-4Mol/L), butter of tin concentration is 3.0 × 10-6~8.0 × 10-3Mol/L (preferably 2.8 × 10-5~2.2
×10-4Mol/L), the dipping solution volumetric usage is calculated as 0.5~5.5mL/g (preferably 1.2~3.6mL/g) with carrier quality.
Further, described Pt-Sn/SiO2The renovation process of loaded catalyst is off into hydrogenating materials, continues logical
Enter hydrogen, be 100~1000h in 300 DEG C~600 DEG C of temperature, 0.8~6.0MPa of pressure, hydrogen volume air speed-1Under the conditions of to lose
Catalyst living carries out 3~24h of hydrogenation regeneration in reactor.
Further, described reaction is carried out in the reactor of two or more serial or parallel connections, each reactor
The identical or different catalyst of interior filling.
The used optional fixed bed of reactor of present invention reaction, expanded bed, fluid bed, stirred-tank reactor, and
Catalytic distillation reactor.Reaction unit can have multiple reactors to operate in parallel or series.Material in reactor can be taken
Upstriker, it would however also be possible to employ downstriker.
A kind of beneficial effect of method for reducing linear alkylbenzene (LAB) unsaturated hydrocarbons content of the present invention is mainly reflected in：
(1) technological process is simple, substitutes bleaching earth adsorption and refines, the pollution environment that spent bleaching clay landfill disposal can be avoided to cause；
(2) catalyst activity stability is good, and the device stable operation time is long, and reactor reaction and regeneration can be avoided frequently to cut
Operation is changed, linear alkylbenzene (LAB) loss is few；
(3) catalyst is renewable, and a large amount of dead catalyst can be avoided to post-process, and effect on environment is small.
(4) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
ZCX-2 types, 20~40 mesh Bio-sils of silica gel used for the production of Qingdao Haiyang chemical company in embodiment,
Liquid volume compares 50 with solid masses:Under the conditions of 1 (mL/g), 80 DEG C of temperature, with the aqueous solution of nitric acid of mass concentration 10% to it
8h is handled, is separated by filtration；Filter cake compares 50 in liquid volume and solid masses:By 2 steamings under the conditions of 1 (mL/g), 80 DEG C of temperature
Distilled water agitator treating 3h, it is separated by filtration, 120 DEG C of dry 3h, then respectively through 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C of roasting 1h,
The SiO handled2, it is used as catalyst carrier.
Chloroplatinic acid (H2PtCl6.6H2O), pure, the factory of Shanghai reagent one is analyzed；Citric acid, analyzes pure, the examination of Zhejiang culminant star chemical industry
Agent Co., Ltd；Butter of tin (SnCl4.5H2O), chemical pure, Nanjing chemical reagent work；Hydrochloric acid, analyzes pure, the double woods chemical reagents in Hangzhou
Factory.Hydrogen comes from Hangzhou Jin Gong special gases Co., Ltd, the equal ＞ 99.99% of purity.
Use the stainless steel tubular type reactor size of fixed-bed reactor for：Internal diameter 10mm, external diameter 14mm, long 100cm,
By Catalyst packing portion in the reactor, inertia quartz sand is filled up at reactor two ends.Reaction temperature by temperature control instrument control,
By back pressure valve regulation hydrogenation reaction pressure.
The PRA-100Br type bromine indexs analyzer produced using Jiangsu Jianghuan Analyser Co., Ltd. determines reaction raw materials
With the bromine index of product, hydrogenation reaction olefin conversion is calculated by the difference of raw material and product bromine index, divided by raw material bromine index.
Hydrogenation reaction raw material 1 is benzene and C10~C14Linear alkene alkylation mixture is through isolated straight of vacuum distillation
Alkyl group benzene, its bromine index is 227.63mgBr/100g.
Hydrogenation reaction raw material 2 is benzene and C10~C14Linear alkene alkylation mixture is through isolated straight of vacuum distillation
Alkyl group benzene, its bromine index is 28.18mgBr/100g.
Hydrogenation reaction raw material 3 is benzene and C10~C14Linear alkene alkylation mixture is through isolated straight of vacuum distillation
Alkyl group benzene, its bromine index is 493.52mgBr/100g.
Hydrogenation reaction raw material 4 is benzene and C10~C14Linear alkene alkylation mixture, its benzene, linear alkylbenzene (LAB), C10~C14
The mass fraction of linear paraffin is respectively 52.48%, 6.65%, 40.87%, and bromine index is 315.18mgBr/100g.
Hydrogenation reaction raw material 5 is benzene and C10~C14Linear alkene alkylation mixture, its benzene, linear alkylbenzene (LAB), C10~C14
The mass fraction of linear paraffin is respectively 15.71%, 11.87%, 72.42%, and bromine index is 516.25mgBr/100g.
Hydrogenation reaction raw material 6 is benzene and C10~C14Linear alkene alkylation mixture, its benzene, linear alkylbenzene (LAB), C10~C14
The mass fraction of linear paraffin is respectively 57.46%, 5.99%, 36.55%, and bromine index is 37.67mgBr/100g.The present invention
The room temperature is 25 DEG C.
Embodiment 1：0.2%Pt-0.4%Sn/SiO2Catalyst preparation
Weigh 10g Bio-sil carrier (its specific surface area be 480m2/g).By 0.0531g (1.0253 × 10-4mol)
Chloroplatinic acid and HCl mass fractions configure 6mL solution As for 2% aqueous hydrochloric acid solution.By 0.1181g (3.3685 × 10-4Mol) four
Stannic chloride and HCl mass fractions configure 6mL solution Bs for 2% aqueous hydrochloric acid solution.Under nitrogen protection, stirring, room temperature condition,
B solution is slowly dropped in solution A, chloroplatinic acid and butter of tin concentration difference in 12mL dipping solutions, dipping solution is formed
For 8.5441 × 10-6Mol/mL and 2.8071 × 10-5Mol/mL, dipping solution volume and catalyst carrier maximum adsorption water
Volume is equal；2h is stood after 12mL dipping solutions, completion of dropping are added dropwise while stirring into 10g silica gel；Then, done at 80 DEG C
Dry 24h, is warming up to 450 DEG C, constant temperature calcining 10h obtains solid with 1 DEG C/min rate program；Compare 10 in water and solid volume:
Under the conditions of 1, with 160mL distilled water agitator treating 8h, it is separated by filtration, repeated washing and filtering 10 times, then through being dried at 80 DEG C
24h, is warming up to 200 DEG C, constant temperature calcining 10h obtains catalyst precursors with 1 DEG C/min rate program.Finally, reaction is taken
The mode of reduction in device pipe, in pressure 0.2MPa, hydrogen volume air speed 2000h-1, 120 DEG C of bars are warming up to 1 DEG C/min speed
8h is reduced under part, it is respectively 0.2% and 0.4% to obtain Pt and Sn mass fractions, the ratio between Pt and Sn mass fractions are 0.5:1 it is negative
Supported catalyst, is designated as 0.2%Pt-0.4%Sn/SiO2。
Embodiment 2：0.5%Pt-0.5%Sn/SiO2Catalyst preparation
Weigh 10g Bio-sil carrier.By 0.1327g (2.5623 × 10-4Mol) chloroplatinic acid and HCl mass fractions are
5% aqueous hydrochloric acid solution configuration 6mL solution As.By 0.1477g (4.2128 × 10-4Mol) butter of tin and HCl mass fractions are
5% aqueous hydrochloric acid solution configuration 6mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped to solution A
In, 12mL dipping solutions are formed, chloroplatinic acid and butter of tin concentration are respectively 2.1352 × 10 in dipping solution-5Mol/mL and
3.5106×10-5Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water；The side into 10g silica gel
Stir after 12mL dipping solutions, completion of dropping is added dropwise in side and stand 10h；Then, 2h is dried at 100 DEG C, with 10 DEG C/min speed
Rate temperature programming is to 600 DEG C, constant temperature calcining 1h；Compare 50 in water and solid volume:Under the conditions of 1, with 800mL distilled water agitator treatings
3h, is separated by filtration, repeated washing and filtering 2 times, then through drying 2h at 100 DEG C, 400 are warming up to 10 DEG C/min rate program
DEG C, constant temperature calcining 1h obtains catalyst precursors.Finally, the mode of reduction in reactor tube is taken, in pressure 3.0MPa, hydrogen
Air volume air speed 100h-1, be warming up to 5 DEG C/min speed under the conditions of 250 DEG C and reduce 1h, obtain Pt and Sn mass fractions difference
It is 1 for the ratio between 0.5% and 0.5%, Pt and Sn mass fractions:1 loaded catalyst, is designated as 0.5%Pt-0.5%Sn/
SiO2。
Embodiment 3：1%Pt-0.5%Sn/SiO2Catalyst preparation
Weigh 10g Bio-sil carrier.By 0.2654g (5.1246 × 10-4Mol) chloroplatinic acid and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 6mL solution As.By 0.1477g (4.2128 × 10-4Mol) butter of tin and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 6mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped to A molten
In liquid, 12mL dipping solutions are formed, chloroplatinic acid and butter of tin concentration are respectively 4.2704 × 10 in dipping solution-5Mol/mL and
3.5106×10-5Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water；The side into 10g silica gel
Stir after 12mL dipping solutions, completion of dropping is added dropwise in side and stand 24h；Then, 24h is dried at 80 DEG C, with 5 DEG C/min speed
Temperature programming is to 600 DEG C, constant temperature calcining 1h；Compare 20 in water and solid volume:Under the conditions of 1, with 320mL distilled water agitator treatings
8h, is separated by filtration, repeated washing and filtering 5 times, then through drying 24h at 80 DEG C, 200 are warming up to 1 DEG C/min rate program
DEG C, constant temperature calcining 10h obtains catalyst precursors.Finally, the mode of reduction in reactor tube is taken, in pressure 1.0MPa, hydrogen
Air volume air speed 200h-1, be warming up to 2 DEG C/min speed under the conditions of 150 DEG C and reduce 8h, obtain Pt and Sn mass fractions difference
It is 2 for the ratio between 1% and 0.5%, Pt and Sn mass fractions:1 loaded catalyst, is designated as 1%Pt-0.5%Sn/SiO2。
Embodiment 4：3%Pt-3%Sn/SiO2Catalyst preparation
Weigh 10g Bio-sil carrier.By 0.7962g (1.5374 × 10-3Mol) chloroplatinic acid and HCl mass fractions are
20% aqueous hydrochloric acid solution configuration 6mL solution As.By 0.8862g (2.5277 × 10-3Mol) butter of tin and HCl mass fractions are
20% aqueous hydrochloric acid solution configuration 7mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped to A molten
In liquid, 12mL dipping solutions are formed, chloroplatinic acid and butter of tin concentration are respectively 1.2811 × 10 in dipping solution-4Mol/mL and
2.1064×10-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water；The side into 10g silica gel
Stir after 12mL dipping solutions, completion of dropping is added dropwise in side and stand 24h；Then, 4h is dried at 100 DEG C, with 1 DEG C/min speed
Temperature programming is to 450 DEG C, constant temperature calcining 10h；Compare 30 in water and solid volume:Under the conditions of 1, with 480mL distilled water agitator treatings
5h, is separated by filtration, repeated washing and filtering 5 times, then through drying 20h at 90 DEG C, 200 are warming up to 2 DEG C/min rate program
DEG C, constant temperature calcining 10h obtains catalyst precursors.Finally, the mode of reduction in reactor tube is taken, in pressure 1.0MPa, hydrogen
Air volume air speed 1000h-1, be warming up to 2 DEG C/min speed under the conditions of 180 DEG C and reduce 6h, obtain Pt and Sn mass fractions equal
It is 1 for the ratio between 3.0%, Pt and Sn mass fractions:1 loaded catalyst, is designated as 3%Pt-3%Sn/SiO2。
Embodiment 5：5%Pt-2.5%Sn/SiO2Catalyst preparation
Weigh 10g Bio-sil carrier.By 1.327g (2.5623 × 10-3Mol) chloroplatinic acid and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 6mL solution As.By 0.7385g (2.1064 × 10-3Mol) butter of tin and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 6mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped to A molten
In liquid, 12mL dipping solutions are formed, chloroplatinic acid and butter of tin concentration are respectively 2.1352 × 10 in dipping solution-4Mol/mL and
1.7553×10-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water；To 10g Bio-sils
8h is stood after 12mL dipping solutions, completion of dropping are added dropwise while stirring in carrier；Then, 8h is dried at 90 DEG C, with 2 DEG C/min
Rate program be warming up to 550 DEG C, constant temperature calcining 4h；Compare 20 in water and solid volume:Under the conditions of 1, stirred with 320mL distilled water
8h is washed, is separated by filtration, repeated washing and filtering 5 times, then through drying 24h at 80 DEG C, be warming up to 1 DEG C/min rate program
200 DEG C, constant temperature calcining 10h obtains catalyst precursors.Finally, the mode of reduction in reactor tube is taken, in pressure
3.0MPa, hydrogen volume air speed 2000h-1, be warming up to 250 DEG C with 5 DEG C/min speed under the conditions of reductase 12 h, obtain Pt and Sn matter
Amount fraction is respectively that the ratio between 5% and 2.5%, Pt and Sn mass fractions are 2:1 loaded catalyst, is designated as 5%Pt-2.5%
Sn/SiO2。
Embodiment 6：3%Pt-3%Sn/SiO2- L1 catalyst preparations
Weigh 10g Bio-sil carrier.By 0.7962g (1.5374 × 10-3Mol) chloroplatinic acid, 0.3231g (1.5374
×10-3Mol) citric acid and HCl mass fractions configure 6mL solution As, citric acid and chloroplatinic acid mole for 10% aqueous hydrochloric acid solution
Than for 1:1.By 0.8862g (2.5277 × 10-3Mol) butter of tin and HCl mass fractions configure for 10% aqueous hydrochloric acid solution
6mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped in solution A, 12mL dippings are formed molten
Chloroplatinic acid, butter of tin and citric acid concentration are respectively 1.2811 × 10 in liquid, dipping solution-4mol/mL、2.1064×10- 4Mol/mL and 1.2812 × 10-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water；To 10g
24h is stood after 12mL dipping solutions, completion of dropping are added dropwise while stirring in Bio-sil carrier；Then, dried at 100 DEG C
4h, 500 DEG C, constant temperature calcining 10h are warming up to 1 DEG C/min rate program；Compare 20 in water and solid volume:Under the conditions of 1, use
320mL distilled water agitator treating 8h, are separated by filtration, repeated washing and filtering 5 times, then through drying 24h at 80 DEG C, with 1 DEG C/min
Rate program be warming up to 200 DEG C, constant temperature calcining 10h obtains catalyst precursors.Finally, the mode of reduction in pipe is taken,
Pressure 1.0MPa, hydrogen volume air speed 1000h-1, be warming up to 2 DEG C/min speed under the conditions of 180 DEG C and reduce 6h, obtain Pt and
Sn mass fractions are that the ratio between 3.0%, Pt and Sn mass fractions are 1:1 loaded catalyst, is designated as 3%Pt-3%Sn/
SiO2-L1。
Embodiment 7：3%Pt-3%Sn/SiO2- L4 catalyst preparations
Weigh 10g Bio-sil carrier.By 0.7962g (1.5374 × 10-3Mol) chloroplatinic acid, 1.2924g (6.1502
×10-3Mol) citric acid and HCl mass fractions configure 6mL solution As, citric acid and chloroplatinic acid mole for 10% aqueous hydrochloric acid solution
Than for 4:1.By 0.8862g (2.5277 × 10-3Mol) butter of tin and HCl mass fractions configure for 10% aqueous hydrochloric acid solution
6mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped in solution A, 12mL dippings are formed molten
Chloroplatinic acid, butter of tin and citric acid concentration are respectively 1.2811 × 10 in liquid, dipping solution-4mol/mL、2.1064×10- 4Mol/mL and 5.1252 × 10-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water；To silicon
24h is stood after dipping solution, completion of dropping is added dropwise in glue while stirring；Then, 4h is dried at 100 DEG C, with 1 DEG C/min speed
Rate temperature programming is to 500 DEG C, constant temperature calcining 10h；Compare 20 in water and solid volume:Under the conditions of 1, washed with the stirring of 320mL distilled water
8h is washed, is separated by filtration, repeated washing and filtering 5 times, then through drying 24h at 80 DEG C, be warming up to 1 DEG C/min rate program
200 DEG C, constant temperature calcining 10h obtains catalyst precursors.Finally, the mode of reduction in reactor tube is taken, in pressure
1.0MPa, hydrogen volume air speed 1000h-1, be warming up to 2 DEG C/min speed under the conditions of 180 DEG C and reduce 6h, obtain Pt and Sn matter
Amount fraction is that the ratio between 3.0%, Pt and Sn mass fractions are 1:1 loaded catalyst, is designated as 3%Pt-3%Sn/SiO2-
L4。
Embodiment 8：3%Pt-3%Sn/SiO2- U30 catalyst preparations
Weigh 10g Bio-sil carrier.By 0.7962g (1.5374 × 10-3Mol) chloroplatinic acid and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 6mL solution As.By 0.8862g (2.5277 × 10-3Mol) butter of tin and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 6mL solution Bs.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped to A molten
In liquid, 12mL dipping solutions are formed, chloroplatinic acid and butter of tin concentration are respectively 1.2811 × 10 in dipping solution-4Mol/mL and
2.1064×10-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water.In city of Kunshan's Ultrasound Instrument
In the KQ-100DE type numerical control ultrasonic cleaners of device Co., Ltd production, dipping solution is added dropwise to carrier in room temperature beaker,
And be stirred continuously；Drip after dipping solution, it is ultrasonically treated under the conditions of room temperature, supersonic frequency 40kHz, ultrasonic power 30W
60min；6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；550 DEG C are warming up to 5 DEG C/min rate programs, 4h is calcined；In water
Compare 20 with solid volume:Under the conditions of 1, with 320mL distilled water agitator treating 8h, it is separated by filtration, repeated washing and filtering 5 times, then
Through drying 24h at 80 DEG C, 200 DEG C are warming up to 1 DEG C/min rate program, constant temperature calcining 10h obtains catalyst precursors.
Finally, the mode of reduction in reactor tube is taken, in pressure 1.0MPa, hydrogen volume air speed 1000h-1, with 2 DEG C/min speed
6h is reduced under the conditions of being warming up to 180 DEG C, it is that the ratio between 3.0%, Pt and Sn mass fractions are 1 to obtain Pt and Sn mass fractions:1
Loaded catalyst, is designated as 3%Pt-3%Sn/SiO2-U30。
Embodiment 9：3%Pt-3%Sn/SiO2- U100 catalyst preparations
Weigh 10g Bio-sil carrier.By 0.7962g (1.5374 × 10-3Mol) chloroplatinic acid and HCl mass fractions are
10% aqueous hydrochloric acid solution configuration 18mL solution As.By 0.8862g (2.5277 × 10-3Mol) butter of tin and HCl mass fractions
18mL solution Bs are configured for 10% aqueous hydrochloric acid solution.Under nitrogen protection, stirring, room temperature condition, B solution is slowly dropped to A
In solution, 36mL dipping solutions are formed, chloroplatinic acid and butter of tin concentration are respectively 4.2706 × 10 in dipping solution-5mol/mL
With 7.0214 × 10-5Mol/mL, dipping solution volume is 3 times of catalyst carrier maximum adsorption water volume.In city of Kunshan's ultrasound
In the KQ-100DE type numerical control ultrasonic cleaners of Instrument Ltd.'s production, it is added dropwise in room temperature beaker to carrier and impregnates molten
Liquid, and be stirred continuously；Drip after dipping solution, under the conditions of room temperature, supersonic frequency 40kHz, ultrasonic power 100W at ultrasound
Manage 10min；6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；550 DEG C are warming up to 5 DEG C/min rate programs, 4h is calcined；
Water compares 20 with solid volume:Under the conditions of 1, with 320mL distilled water agitator treating 8h, it is separated by filtration, repeated washing and filtering 5 times,
Again through drying 24h at 80 DEG C, 200 DEG C are warming up to 1 DEG C/min rate program, constant temperature calcining 10h obtains complex catalyst precursor
Thing.Finally, the mode of reduction in reactor tube is taken, in pressure 1.0MPa, hydrogen volume air speed 1000h-1, with 2 DEG C/min's
Speed reduces 6h under the conditions of being warming up to 180 DEG C, and it is that the ratio between 3.0%, Pt and Sn mass fractions are to obtain Pt and Sn mass fractions
1:1 loaded catalyst, is designated as 3%Pt-3%Sn/SiO2-U100。
Embodiment 10：Catalyst performance evaluation
Using fixed-bed reactor, in 250 DEG C of temperature, pressure 2.0MPa, hydrogen to oil volume ratio 1000:1st, liquid quality is empty
Fast 1.0h-1Reaction condition under, the catalytic hydrogenation reaction of different catalysts is carried out with hydrogenation reaction raw material 1 (linear alkylbenzene (LAB)),
Experimental result is shown in Table 1.
The catalytic hydrogenation reaction result under different catalysts effect of table 1
| Catalyst | Bromine index, mgBr/100g | Olefin conversion, % |
| 0.2%Pt-0.4%Sn/SiO2 | 73.38 | 67.76 |
| 0.5%Pt-0.5%Sn/SiO2 | 26.16 | 88.51 |
| 1%Pt-0.5%Sn/SiO2 | 17.22 | 92.44 |
| 3%Pt-3%Sn/SiO2 | 14.03 | 93.84 |
| 5%Pt-2.5%Sn/SiO2 | 11.82 | 94.81 |
| 3%Pt-3%Sn/SiO2-L1 | 12.33 | 94.58 |
| 3%Pt-3%Sn/SiO2-L4 | 12.06 | 94.70 |
| 3%Pt-3%Sn/SiO2-U30 | 12.85 | 94.35 |
| 3%Pt-3%Sn/SiO2-U100 | 12.27 | 94.61 |
As it can be seen from table 1 as catalyst Pt load capacity increases, hydrogenation products bromine index reduces, olefin hydrogenation
Conversion ratio is improved, and catalyst activity is gradually stepped up.Compare identical Pt load capacity catalyst hydrogenation activity, with complexing infusion process and super
Catalyst activity prepared by sound infusion process increases, and illustrates that complexing dipping and ultrasonic immersing are conducive to improving Pt-Sn/SiO2It is negative
The activity of supported catalyst.
In addition, by carrying out color-matter combination analysis to hydrogenating materials and hydrogenation products, it was demonstrated that catalytic hydrogenation operation does not occur
Benzene ring hydrogenation and cracking reaction, in the absence of hydrogenation selectivity problem.
Embodiment 11：Hydrogenation conditions are investigated
Using fixed-bed reactor, in 3%Pt-3%Sn/SiO2Under-L1 catalyst actions, with hydrogenation reaction raw material 1
(linear alkylbenzene (LAB)) carries out the catalytic hydrogenation reaction of different condition, single factor exploration temperature, pressure, mass space velocity, hydrogen oil volume
The reaction condition influence of ratio, experimental result is shown in Table 2.As known from Table 2, as reaction temperature is improved, pressure increases, mass space velocity drops
Low, hydrogen to oil volume ratio increase, hydrogenation products bromine index is gradually reduced, hydrogenation conversion increase, that is, is hydrogenated with effect and is improved.
Table 2 investigates the experimental result of hydrogenation conditions influence
Color-matter combination analysis is carried out to the hydrogenation products of hydrogenating materials and the condition of table 2, it was demonstrated that catalytic hydrogenation operation does not occur
Benzene ring hydrogenation and cracking reaction, in the absence of hydrogenation selectivity problem.
Embodiment 12：The reaction result of different hydrogenating materials compares
Using fixed-bed reactor, in 3%Pt-3%Sn/SiO2Under-L1 catalyst actions, in 200 DEG C of temperature, pressure
2.0MPa, mass space velocity 1.0h-1, hydrogen to oil volume ratio 1000:Under 1 reaction condition, (it is hydrogenated with three kinds of linear alkylbenzene (LAB)s respectively
Reaction raw materials 1, hydrogenation reaction raw material 2 and hydrogenation reaction raw material 3) carry out continuing catalytic hydrogenation reaction, experimental result is shown in Table 3.
Using fixed-bed reactor, in 3%Pt-3%Sn/SiO2Under-L1 catalyst actions, in 100 DEG C of temperature, pressure
2.0MPa, mass space velocity 1.0h-1, hydrogen to oil volume ratio 1000:Under 1 reaction condition, respectively with three kinds of alkylation mixtures (i.e. plus
Hydrogen reaction raw materials 4, hydrogenation reaction raw material 5 and hydrogenation reaction raw material 6) carry out continuing catalytic hydrogenation reaction, experimental result is shown in Table 4.
3 three kinds of straight chained alkyl benzene hydrogenation results of table
4 three kinds of alkylation mixture hydrogenation reaction results of table
In table 3 bromine index of three kinds of straight chained alkyl benzene hydrogenation raw materials 1,2 and 3 be respectively 227.63mgBr/100g,
28.18mgBr/100g, 493.52mgBr/100g, under identical hydrogenation conditions, olefin conversion is with hydrogenating materials
Bromine index increases and increased.The bromine index of three kinds of alkylation mixture hydrogenating materials 4,5 and 6 is respectively 315.18mgBr/ in table 4
100g, 516.25mgBr/100g, 37.67mgBr/100g, equally under identical hydrogenation conditions, olefin conversion with
Hydrogenating materials bromine index increases and increased.
Knowable to comparison sheet 3 and the data of table 4, other hydrogenation conditions identical situations close in hydrogenating materials bromine index
Under, three kinds of alkylation mixture hydrogenating materials are by 100 DEG C of hydrogenation reactions, higher than three kinds straight chained alkyl benzene hydrogenations of olefin conversion
Olefin conversion of the raw material through 200 DEG C of hydrogenation reactions.Olefin hydrogenation easily occurs for this explanation, alkylation mixture, and straight
Alkyl group benzene needs to carry out olefin hydrogenation at a higher temperature.A kind of process technology scheme that can be taken is alkylation mixing
Thing then carries out separated and obtains linear alkyl benzene product by the hydrogenation reaction removing unsaturated hydrocarbons of lower temperature.Another work
Skill scheme is first to obtain linear alkylbenzene (LAB) through alkylation mixture separated, then carries out the catalytic hydrogenation reaction of higher temperature and obtain
To linear alkylbenzene (LAB) refined products.
Reacted by lasting 1000h, the hydrogenation products bromine index and alkene of linear alkylbenzene (LAB) and alkylation mixture raw material
Conversion ratio change is little, illustrates that the activity stability of catalyst is preferable.
Embodiment 13：Hydrogenation catalyst regenerates and its performance evaluation
Using two sets of fixed-bed reactors, in 3%Pt-3%Sn/SiO2Under-L1 catalyst actions, reaction condition includes
Pressure 2.0MPa, mass space velocity 1.0h-1, hydrogen to oil volume ratio 1000:1.A set of reaction unit (straight chain alkane of hydrogenation reaction raw material 1
Base benzene) 200 DEG C of catalytic hydrogenation reactions are persistently carried out, treat that hydrogenation products bromine index brings up to 30mgBr/100g, olefin conversion drop
It is low to stop input hydrogenation reaction raw material to 86.82%；Regeneration stage is hydrogenated with into decaying catalyst, continues to be passed through hydrogen, in pressure
Power 6.0MPa, hydrogen volume air speed 100h-1Under the conditions of, temperature is increased to 300 DEG C of constant temperature and regenerates 3h, then temperature is brought up to
600 DEG C of constant temperature regenerate 24h.Then, in 200 DEG C of temperature, pressure 2.0MPa, mass space velocity 1.0h-1, hydrogen to oil volume ratio 1000:1 is anti-
Input hydrogenation reaction raw material 1, persistently carries out catalytic hydrogenation reaction, is as a result listed in table 5 under the conditions of answering.
Another set of reaction unit persistently carries out 100 DEG C of catalytic hydrogenation reactions with hydrogenation reaction raw material 4 (alkylation mixture),
Treat that hydrogenation products bromine index brings up to 30mgBr/100g, it is former that olefin conversion is reduced to 90.48% stopping input hydrogenation reaction
Material；Regeneration stage is hydrogenated with into decaying catalyst, continues to be passed through hydrogen, in pressure 0.8MPa, hydrogen volume air speed 1000h-1Bar
Under part, temperature is increased to 300 DEG C of constant temperature and regenerates 3h, then temperature is brought up into 500 DEG C of constant temperature regeneration 21h.Then, in temperature
100 DEG C, pressure 2.0MPa, mass space velocity 1.0h-1, hydrogen to oil volume ratio 1000:Hydrogenation reaction raw material 4 is inputted under 1 reaction condition, is held
It is continuous to carry out catalytic hydrogenation reaction, as a result together it is listed in table 5.
The performance evaluation of the regenerated catalyst of table 5
As known from Table 5, reaction unit 1 passes through catalyst regenerative operation, the hydrogenated olefin conversion ratios of hydrogenating materials 1 from
86.82% brings up to 91.83%；Reaction unit 2 passes through catalyst regenerative operation, the hydrogenated olefin conversion ratios of hydrogenating materials 4 from
90.48% brings up to 94.81%.This explanation, inactivation loaded catalyst regenerates by hydrogenation, and catalyst activity obtains substantially extensive
It is multiple.
Comparison sheet 3, table 4, the data of table 5 can be seen that the activity and activity stability and fresh catalyst of regenerated catalyst
Quite.
It is above-mentioned test result indicates that, catalytic hydrogenation reaction method of the invention can be effectively reduced linear alkylbenzene (LAB), with
And benzene and the bromine index and olefin(e) centent of linear alkene alkylation mixture, the high active of hydrogenation catalysis and reaction selectivity of catalyst
Higher, activity stability is good, and can regenerate.The inventive method is to improve the effective ways of linear alkylbenzene (LAB) quality, tool
There is application value.
Claims (8)
1. a kind of method for reducing linear alkylbenzene (LAB) bromine index, it is characterised in that methods described is：In 60~350 DEG C of temperature, pressure
0.3~10.0MPa of power, mass space velocity 0.2~10.0 hour-1, hydrogen to oil volume ratio 300:1~8000:Under conditions of 1, it will be hydrogenated with
Raw material and hydrogen mixing, with Pt-Sn/SiO2Loaded catalyst contact carries out hydrogenation reaction, makes alkene saturation, and then reduce straight
Alkyl group benzene bromine index；Regenerate, recycle through hydrogenation after catalyst inactivation；The hydrogenating materials are one of following：(1) benzene with
C10~C14The linear alkylbenzene (LAB) that linear alkene alkylation mixture is obtained through separated, its bromine index is 20~800mgBr/
100g；(2) benzene and C10~C14Linear alkene alkylation mixture, its benzene and linear alkylbenzene (LAB) mass fraction be respectively 15~
60%th, 5~15%, remaining is C10~C14Linear paraffin, the bromine index of alkylation mixture is 20~800mgBr/100g；Institute
The Pt-Sn/SiO stated2Loaded catalyst is using Pt and Sn as active component, with SiO2For carrier, Pt mass loadings amount is 0.2~
The ratio between 5.0%, Pt and Sn mass loading amounts are 0.5:1~2:1.
2. the method for reduction linear alkylbenzene (LAB) bromine index as claimed in claim 1, it is characterised in that the Pt mass loadings amount is
The ratio between 0.5~3.0%, Pt and Sn mass loading amounts are 1:1~2:1.
3. the method for reduction linear alkylbenzene (LAB) bromine index as claimed in claim 1, it is characterised in that the hydrogenation conditions are
80~300 DEG C of temperature, 0.5~5.0MPa of pressure, feedstock quality air speed 0.5~5.0 hour-1, hydrogen to oil volume ratio 600:1~
6000:1。
4. the method for linear alkylbenzene (LAB) bromine index is reduced as claimed in claim 1, it is characterised in that the Pt-Sn/SiO2Support type
Catalyst is prepared using incipient impregnation method：In the aqueous hydrochloric acid solution that chloroplatinic acid is dissolved in mass concentration 2%~20%, obtain
Platinum acid chloride solution；In the aqueous hydrochloric acid solution that butter of tin is dissolved in mass concentration 2%~20%, butter of tin solution is obtained；
Under nitrogen protection, stirring, room temperature condition, butter of tin solution is slowly dropped in platinum acid chloride solution, dipping solution is formed；To
2~24h of standing after dipping solution, completion of dropping is added dropwise in carrier while stirring；Then, 2~24h is dried at 80~100 DEG C,
450~600 DEG C are warming up to 1~10 DEG C/min rate program, 1~10h of constant temperature calcining obtains solid；In distilled water and admittedly
Body volume ratio 10:1~50:Under the conditions of 1, washing 3~8h of solid is stirred at room temperature with distilled water, is separated by filtration, repeated washing and mistake
Filter 2~10 times, then through drying 2~24h at 80~100 DEG C, 200~400 DEG C are warming up to 1~10 DEG C/min rate program,
1~10h of constant temperature calcining, obtains catalyst precursors；Finally, take the mode of reduction in reactor tube, pressure 0.2~
3.0MPa, 100~2000h of hydrogen volume air speed-1, be warming up to 1~5 DEG C/min speed under the conditions of 120~250 DEG C and reduce 1
~8h, obtains Pt-Sn/SiO2Loaded catalyst；Chloroplatinic acid concentration is 3.0 × 10 in the dipping solution-6~8.0 × 10- 3Mol/L, butter of tin concentration is 3.0 × 10-6~8.0 × 10-3Mol/L, the dipping solution volumetric usage is in terms of carrier quality
For 0.5~5.5mL/g.
5. the method for linear alkylbenzene (LAB) bromine index is reduced as claimed in claim 1, it is characterised in that the Pt-Sn/SiO2Support type
Catalyst is prepared using complexing dipping method：With citric acid as complexing agent, chloroplatinic acid and citric acid are dissolved in mass concentration 2%
In~20% aqueous hydrochloric acid solution, platinum acid chloride solution is obtained；The hydrochloric acid that butter of tin is dissolved in into mass concentration 2%~20% is water-soluble
In liquid, butter of tin solution is obtained；Under nitrogen protection, stirring, room temperature condition, butter of tin solution is slowly dropped to chlorine platinum
In acid solution, dipping solution is formed；Dipping solution is added dropwise while stirring into carrier, 2~24h is stood；Then, 80~100
2~24h is dried at DEG C, 450~600 DEG C are warming up to 1~10 DEG C/min rate program, 1~10h of constant temperature calcining, consolidate
Body；Compare 10 in distilled water and solid volume:1~50:Under the conditions of 1, washing 3~8h of solid, filtering point are stirred at room temperature with distilled water
From, repeated washing and filtering 2~10 times, then through drying 2~24h at 80~100 DEG C, with 1~10 DEG C/min rate program liter
Temperature is to 200~400 DEG C, and 1~10h of constant temperature calcining obtains catalyst precursors；Finally, the mode of reduction in reactor tube is taken,
In 0.2~3.0MPa of pressure, 100~2000h of hydrogen volume air speed-1, with 1~5 DEG C/min speed be warming up to 120~250 DEG C
Under the conditions of reduce 1~8h, obtain Pt-Sn/SiO2Loaded catalyst；The ratio between amount of the citric acid and chloroplatinic acid material is 1:
1~4:1, chloroplatinic acid concentration is 3.0 × 10 in the dipping solution-6~8.0 × 10-3Mol/L, butter of tin concentration be 3.0 ×
10-6~8.0 × 10-3Mol/L, the dipping solution volumetric usage is calculated as 0.5~5.5mL/g with carrier quality.
6. the method for linear alkylbenzene (LAB) bromine index is reduced as claimed in claim 1, it is characterised in that the Pt-Sn/SiO2Support type
Catalyst is prepared using ultrasonic immersing method：In the aqueous hydrochloric acid solution that chloroplatinic acid is dissolved in mass concentration 2%~20%, chlorine is obtained
Platinic acid solution；In the aqueous hydrochloric acid solution that butter of tin is dissolved in mass concentration 2%~20%, butter of tin solution is obtained；In nitrogen
Under gas shielded, stirring, room temperature condition, butter of tin solution is slowly dropped in platinum acid chloride solution, dipping solution is formed；To load
Dipping solution is added dropwise in body while stirring, adds after dipping solution, in room temperature, supersonic frequency 40kHz, 30~100W of ultrasonic power
Under the conditions of ultrasonically treated 10~60min, stand 2~24h；Then, 2~24h is dried at 80~100 DEG C, with 1~10 DEG C/min
Rate program be warming up to 450~600 DEG C, 1~10h of constant temperature calcining obtains solid；Compare 10 in distilled water and solid volume:1~
50:Under the conditions of 1, washing 3~8h of solid is stirred at room temperature with distilled water, is separated by filtration, repeated washing and filtering 2~10 times, then pass through
2~24h is dried at 80~100 DEG C, 200~400 DEG C are warming up to 1~10 DEG C/min rate program, 1~10h of constant temperature calcining,
Obtain catalyst precursors；Finally, the mode of reduction in reactor tube is taken, in 0.2~3.0MPa of pressure, hydrogen volume air speed
100~2000h-1, be warming up to 120~250 DEG C with 1~5 DEG C/min speed under the conditions of reduce 1~8h, obtain Pt-Sn/SiO2
Loaded catalyst；Chloroplatinic acid concentration is 3.0 × 10 in the dipping solution-6~8.0 × 10-3Mol/L, butter of tin concentration
For 3.0 × 10-6~8.0 × 10-3Mol/L, the dipping solution volumetric usage is calculated as 0.5~5.5mL/g with carrier quality.
7. the method for linear alkylbenzene (LAB) bromine index is reduced as claimed in claim 1, it is characterised in that described Pt-Sn/SiO2Load
The renovation process of type catalyst is off into hydrogenating materials, continues to be passed through hydrogen, 300 DEG C~600 DEG C of temperature, pressure 0.8~
6.0MPa, hydrogen volume air speed are 100~1000h-1Under the conditions of to decaying catalyst carry out reactor in hydrogenation regeneration 3~24h.
8. the method for linear alkylbenzene (LAB) bromine index is reduced as claimed in claim 1, it is characterised in that described reaction is at two
Or carried out in the reactor of two or more serial or parallel connection, the identical or different catalyst of filling in each reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511029447.2A CN105503495B (en) | 2015-12-31 | 2015-12-31 | A kind of method for reducing linear alkylbenzene (LAB) bromine index |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511029447.2A CN105503495B (en) | 2015-12-31 | 2015-12-31 | A kind of method for reducing linear alkylbenzene (LAB) bromine index |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105503495A CN105503495A (en) | 2016-04-20 |
| CN105503495B true CN105503495B (en) | 2017-10-20 |
Family
ID=55711873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511029447.2A Active CN105503495B (en) | 2015-12-31 | 2015-12-31 | A kind of method for reducing linear alkylbenzene (LAB) bromine index |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105503495B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7863489B2 (en) * | 2008-07-31 | 2011-01-04 | Celanese International Corporation | Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst |
| US8501652B2 (en) * | 2008-07-31 | 2013-08-06 | Celanese International Corporation | Catalysts for making ethanol from acetic acid |
| CN103304360B (en) * | 2012-03-15 | 2015-01-14 | 清华大学 | Butadiene product and preparation method thereof |
| CN103012034B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Method for removing micro-quantity alkene in aromatic hydrocarbon |
| CN104107701B (en) * | 2013-04-16 | 2016-08-03 | 中国石油化工股份有限公司 | High activity Pt base catalyst, preparation method and its usage |
| CN104342201B (en) * | 2013-08-09 | 2017-03-01 | 中国石油天然气股份有限公司 | Method for removing olefin by hydrogenation of reformate |
| CN104342200B (en) * | 2013-08-09 | 2016-05-11 | 中国石油天然气股份有限公司 | Method for selective hydrogenation of reformate |
-
2015
- 2015-12-31 CN CN201511029447.2A patent/CN105503495B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105503495A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105669347B (en) | A kind of method for reducing linear alkylbenzene (LAB) unsaturated hydrocarbons content | |
| CN103012034B (en) | Method for removing micro-quantity alkene in aromatic hydrocarbon | |
| CN1088449C (en) | Process for alkylating hydrocarbons | |
| CN104525195B (en) | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof | |
| CN107088436A (en) | Selective hydrogenation of acetylene prepares the catalyst and preparation method and application of ethene | |
| CN102614870B (en) | Vinylacetylene hydrogenation catalyst and preparation method thereof | |
| CN101397230B (en) | C5 and/or C6 alkane isomerization process | |
| CN105601463B (en) | A kind of method of linear alkylbenzene (LAB) Hydrobon | |
| CN1230942A (en) | Selective catalytic conversion of C9 aromatic feedstock containing substantial amounts of ethyl substituted aromatic components to product rich in toluene and/or xylenes | |
| CN103769076B (en) | Method for preparing olefin-removal catalyst by taking clay as raw materials | |
| CN109529827A (en) | A kind of alumina support, preparation method containing carried catalyst and catalyst application | |
| CN103495435B (en) | A kind of catalyst for removing olefins from reforming oil and preparation method thereof | |
| CN106608790A (en) | Method for production of ethylene through selective hydrogenation of acetylene | |
| CN105503495B (en) | A kind of method for reducing linear alkylbenzene (LAB) bromine index | |
| CN106268792A (en) | A kind of attapulgite clay basic weight is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application | |
| CN1701848A (en) | Preparation of supported amorphous catalyst for pre-hydrogenation of coked crude benzol | |
| CN105601464B (en) | A kind of catalytic hydrogenation method for reducing linear alkylbenzene (LAB) bromine index | |
| CN109529811A (en) | Alumina support, salic carried catalyst preparation method and catalyst application | |
| CN106365941B (en) | Conversion process of low-carbon hydrocarbon | |
| CN102794178A (en) | Selective hydrogenation catalyst and preparation thereof | |
| CN103012037B (en) | Method for removing trace olefin from aromatic hydrocarbon | |
| CN107497424A (en) | A kind of graphene-based catalyst of supported palladium and preparation method thereof | |
| CN1295880A (en) | Selective hydrogenation catalyst for alkyne and diene | |
| CN104588042B (en) | A kind of preparation method of vulcanization type propane dehydrogenation catalyst | |
| CN102319586B (en) | Resin catalyst used in alkylation reaction of isobutene and butylene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |