CN1282733C - Cytalyst for reformed formation oil selective hydrogen removing olefin - Google Patents
Cytalyst for reformed formation oil selective hydrogen removing olefin Download PDFInfo
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- CN1282733C CN1282733C CN 02109413 CN02109413A CN1282733C CN 1282733 C CN1282733 C CN 1282733C CN 02109413 CN02109413 CN 02109413 CN 02109413 A CN02109413 A CN 02109413A CN 1282733 C CN1282733 C CN 1282733C
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- catalyzer
- oil
- selective hydrogenation
- hydrogenation
- metal
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 11
- 239000001257 hydrogen Substances 0.000 title claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 10
- 150000001336 alkenes Chemical class 0.000 title abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- -1 olefin hydrocarbon Chemical class 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002156 adsorbate Substances 0.000 claims description 5
- 230000002860 competitive effect Effects 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002671 adjuvant Substances 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052794 bromium Inorganic materials 0.000 abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention introduces a catalyst for the selective hydrogenation and olefin removal of reformation produced oil. The catalyst comprises noble metals with the weight percentage of 0.1 to 1.0% to be used as active components, and alkali metals or alkaline earth metals with the weight percentage of 0.05 to 0.50% to be used as auxiliary agents. A carrier of catalyst is refractory inorganic oxide. The surface area of the catalyst is from 150 to 250m<2>/g, and the pore capacity of the catalyst is from 0.3 to 0.8 ml/g. The catalyst of the present invention is suitable for the selective hydrogenation and alkene removal of gasoline fraction reformation produced oil. Under the conditions that the reaction temperature is from 150 to 250 DEG C, the pressure is from 1.5 to 3.0MPa, and the volume air speed is from 2.0 to 4.0h<-1>, the bromine index of the product is smaller than 100 mg Br / 100g oil, the weight percentage of the loss of arene is less than 0.5%, and a satisfactory result is obtained.
Description
1, technical field
The invention belongs to the hydrofining of petroleum hydrocarbon product, in particular, it relates to a kind of catalyzer that is mainly used in gasoline fraction reformed oil selective hydrogenation and olefin hydrocarbon removal.
2, background technology
The main effect that catalytic reforming generates oily selective hydrogenation catalyst is to face under the hydrogen state, reformed oil is carried out selective hydrogenation and removing alkene, not by hydrogenation under the saturated situation, realizes that deep hydrogenation deviates from alkene wherein at aromatic hydrocarbons.
Naphtha fraction is rich in aromatic hydrocarbons and a part of solvent oil cut in the generation oil of catalytic reforming, also contain a spot of alkene simultaneously.Reformer for production classes and grades in school BTX aromatic hydrocarbons, all be faced with the problem that how to remove alkene in the reformed oil, because produce qualified industrial chemicals aromatic hydrocarbon product and solvent oil, except carry out extracting with aromatic hydrocarbons with non-aromatics is separated, also must deviate from alkene wherein, otherwise the bromine valency of product, pickling color are defective, this problem is along with the operation operation of Large Scale and Continuous reformation aromatic device, the raising of reaction depth, the increase of olefin(e) centent and more outstanding.In the catalytic reforming unit of high severity, giving birth to olefiant olefin(e) centent will be above 1w%, and the olefin(e) centent of raffinating oil may reach more than the 2w%.
Chang Gui olefin removal method was to adopt carclazyte absorption in the past, but when olefin(e) centent surpasses 1w%, carclazyte absorption requirements (bromine index is less than 100mgBr/100g oil) that be difficult to touch the mark, and the carclazyte absorption life-span cause than short-range missile and change frequently, and carclazyte can not regenerate and reuse.The depleted carclazyte can cause serious environmental to pollute.
Domestic some fixed bed half-regeneration reformer, back end hydrogenation reactor of back series connection of last reactor in the reforming reaction system, adopt conventional Co-Mo or Ni-Mo Hydrobon catalyst, in higher temperature (300～320 ℃) with than low-speed (2～3h
-1) operation down, be difficult to reach degree of depth deolefination (the bromine valency is less than 0.1 gram bromine/100 gram oil) and guarantee that aromatic hydrocarbons does not lose the requirement of (aromatic hydrocarbons loses less than 0.5w%) in hydrogenation process.
Chinese patent CN85100215A has introduced a kind of hydrorefined catalyzer of reforming raffinate oil that is used for, and it is supported on γ-Al by Pt or the Pd of 0.02～0.2w%
2O
3Last formation, this patent application is mentioned in specification sheets: " catalyst activity height; under the mitigation condition, can make the whole hydrogenation of the alkene of raffinating oil saturated; benzene and toluene are had hydrogenation activity normal pressure and about 200 ℃; so this catalyzer not only can be used for the hydrofining of raffinating oil, and also can be used for the hydrofining of reformed oil.Since " about 200 ℃, aromatic hydrocarbons there is hydrogenation activity, so when temperature of reaction was 200 ℃, this catalyzer just can not be used for the selective hydrogenation and removing alkene of reformed oil.Rising along with pressure, beginning has the temperature of hydrogenation activity also to decrease to aromatic hydrocarbons, the hydrorefined pressure that actual capabilities are used, be generally 1.0～3.0MPa, so begin have the temperature of hydrogenation activity must be also lower adding to depress than 200 ℃ to aromatic hydrocarbons, therefore, this catalyzer can not be used for the refining alkene that removes wherein of recapitalization generating oil hydrogenation.
Chinese patent CN85100760A has introduced a kind of hydrofining catalyst for hydrogenation of alkenes and method for making thereof.This catalyzer that is used for the petroleum products hydrogenation of olefins is supported in fiber Al by the Pt of 0.2w%～1w% or Sn or the Pb of Pd or Pd and Pt and 0.05%～2wt%
2O
3Go up made.Yet because fibrous alumina is difficult to be shaped to the Industrial Catalysis agent carrier with certain physical strength at present, much remains to be done so the catalyzer of this invention will be realized industrial application.
3, summary of the invention
At the deficiencies in the prior art, the objective of the invention is to develop a kind of hydrogenation of olefins degree of depth height, aromatic hydrogenation loses few, and the reformed oil selective hydrogenation and olefin hydrocarbon removal catalyzer that the energy long-term stability turns round and the energy industrialization is used.
The major technique characteristics of catalyzer of the present invention are to adopt the porous, inorganic refractory materials, and preferably aluminum oxide prepares the thin shell type catalyzer as support of the catalyst, and its specific surface area is 150～250m
2/ g, pore volume is 0.3～0.8ml/g, have at least and a kind ofly be selected from precious metal in the periodic table of elements group VIII as active metal component, preferably be selected among Pt and the Pd one or both, its content is 0.1w%～1.0w%, is preferably 0.2w%～0.6w%, and have a kind of basic metal or alkaline-earth metal at least as auxiliary agent, preferably be selected among K and Na and the Mg one or both, its content is 0.05w%～0.5w%, is preferably 0.1w%～0.3w%.
The method for making of catalyzer of the present invention can for: described carrier with the solution that contains described active metal component and adjuvant component, in the presence of competitive adsorbate, is flooded preparation.Catalyzer behind the dipping carries out drying under 110～125 ℃, carry out roasting in 400～500 ℃ airflow, reduces in 150～450 ℃ of hydrogen.
The described solution that contains active metal component and adjuvant component generally can be salts solution, nitrate for example, hydrochloride or acylate solution etc.
Described competitive adsorbate can be mineral acid such as nitric acid, hydrochloric acid etc. or organic acid such as trichoroacetic acid(TCA), citric acid etc., and its consumption is generally 0.1w%～1.0w% (is benchmark with the butt alumina amount).
Reactive metal of introducing in the catalyzer of the present invention and auxiliary agent can adopt co-impregnation, also can adopt step impregnation method to prepare.
Catalyzer generally will carry out prevulcanized when using handles.Vulcanizing agent can be organic compounds containing sulfurs such as Methyl disulfide, dithiocarbonic anhydride and thioether.
When catalyzer of the present invention is used for recapitalization generating oil hydrogenation, working conditions is generally: under the condition that hydrogen exists, described reformed oil is contacted with catalyzer hydrogenation reaction takes place, reaction conditions is generally: reaction pressure 1.0～3.0Mpa, 120～250 ℃ of temperature of reaction, hydrogen to oil volume ratio 100～500: volume space velocity 1～8h during 1 liquid
-1, volume space velocity 2～4h when being preferably 150～230 ℃ of hydrogen to oil volume ratio of reaction pressure 1.2～2.0 Mpa temperature of reaction, 200～300: 1 liquid
-1，
The raw material that catalyzer of the present invention was suitable for generally can be the gasoline fraction that contains alkene, and its boiling range scope is generally 60～180 ℃, and aromaticity content is generally 30～80w%, bromine valency 1～10g/100g oil.
Catalyzer of the present invention is used for the selective hydrogenation and olefin hydrocarbon removal process of reformed oil, 150～250 ℃ of temperature.Hydrogen-oil ratio 200～300 (v), air speed 2～4h
-1, under pressure 1.2～2.0MPa condition, the bromine valency that can make the recapitalization generating oil hydrogenation after product is less than 0.1g/100g oil, and aromatic hydrocarbons loses less than 0.5w%, has obtained gratifying result.
4, embodiment
Be further explained in detail the present invention below in conjunction with embodiment.
Embodiment 1
In the presence of the competitive adsorbate hydrochloric acid soln, with content is the platinum of 0.30w% (is benchmark with the butt aluminum oxide) or the salts solution of palladium and platinum and palladium, its concentration is determined (50g) according to the final content of catalyzer, the alumina supporter of dipping different size, roasting all can make catalyzer of the present invention in 4～6 hours in 120 ℃ of dryings 8～10 hours and 450 ℃ of air then.Table 1 has been listed the catalyzer of the inventive method preparation.
The catalyzer of table 1 the present invention preparation
| The catalyzer numbering | Precious metal salt solution | Carrier character | Catalyst metal content w% | |||||
| Surface-area m 2/g | Pore volume ml/g | Bulk density g/ml | Pt | Pd | K | Na | ||
| A | Palladous chloride | 250 | 0.40 | 0.70 | 0.20 | 0.10 | 0.10 | |
| B | Platinic chloride | 180 | 0.51 | 0.75 | 0.25 | 0.20 | ||
| C | Palladous chloride and Platinic chloride | 235 | 0.60 | 0.58 | 0.30 | 0.10 | ||
| D | Platinic chloride | 183 | 0.48 | 0.74 | 0.28 | 0.10 | ||
| E | Palladous chloride and Platinic chloride | 183 | 0.48 | 0.74 | 0.20 | 0.30 | 0.10 | 0.10 |
Embodiment 2
With the catalyzer among the embodiment 1, on the 100ml single hose system, carried out the test of reformed oil selective hydrogenation and olefin hydrocarbon removal.Raw material is that half generative reforming generates oil, and boiling range is 48.8～167.7 ℃, and aromaticity content is 60.5w%, and bromine index is a 1770mgBr/100g oil.Reaction conditions is pressure 2.0MPa, 170 ℃ of temperature, and hydrogen-oil ratio 250, catalyzer reduced 8 hours in 200 ℃ of hydrogen, and using Methyl disulfide prevulcanized, sulfuration amount down at 170 ℃ is the 0.5w% of catalyzer, the results are shown in table 2
Table 2 catalyst reaction performance
| Catalyzer | A | B | C | D | E |
| Aromaticity content, w% | 60.6 | 60.1 | 60.3 | 60.5 | 60.7 |
| Bromine index, mgBr/100g oil | 65 | 62 | 60 | 66 | 61 |
Embodiment 3
With catalyzer C described in the embodiment 1, use the 100ml single hose system, investigated different pressures, selectivity of catalyst hydrogenation and olefin hydrocarbon removal ability.Raw material is that CONTINUOUS REFORMER generates oily BTX cut, and boiling range is 57.6～164.6 ℃, and aromaticity content is 82.81w%, and bromine index is a 2990mgBr/100g oil.Reaction conditions is 1 70 ℃ of temperature, hydrogen-oil ratio 250, air speed 2.0.The results are shown in Table 3.
Table 3 reaction pressure is to the catalyst reaction Effect on Performance
| Reaction pressure Mpa | 1.5 | 2.0 | 2.5 | 3.0 |
| Aromaticity content, w% | 82.60 | 82.71 | 82.43 | 82.5 |
| Bromine index, mgBr/100g oil | 95 | 90 | 84 | 85 |
Embodiment 4
With catalyzer C described in the embodiment 1, on the 100ml single hose system, carried out long-term stable experiment.Test with two kinds of raw materials, a kind of is that embodiment 2 is raw materials used, and another kind is that embodiment 3 is raw materials used.The results are shown in Table 5 and 6.
Table 5 half generative reforming generates oily selective hydrogenation and olefin hydrocarbon removal stability test result
| Runtime, h | Reaction conditions | Generate oil analysis | ||
| Temperature ℃ | Air speed h -1 | Bromine index, mgBr/100g oil | Total aromatic hydrocarbons, w% | |
| 0-152 | 160 | 2.0 | 60 | 60.6 |
| 160-304 | 160 | 4.0 | 122 | 60.2 |
| 312-412 | 170 | 4.0 | 43 | 60.4 |
| 412-512 | 170 | 4.0 | 46 | 60.6 |
| 512-612 | 170 | 4.0 | 47 | 60.7 |
| 612-1012 | 170 | 4.0 | 50 | 60.3 |
| 1012-1512 | 170 | 4.0 | 56 | 60.4 |
| 1512-2000 | 170 | 4.0 | 60 | 60.5 |
| 2000-2600 | 170 | 4.0 | 50 | 60.4 |
Table 6 CONTINUOUS REFORMER generates oily BTX cut stability test result
| Runtime, h | Reaction conditions | Generate oil analysis | ||
| Temperature ℃ | Air speed (v) h -1 | Bromine index mgBr/100g oil | Total aromatic hydrocarbons w% | |
| 0-104 | 160 | 2.0 | 95 | 82.5 |
| 104-192 | 170 | 2.0 | 40 | 82.7 |
| 200-300 | 170 | 3.0 | 70 | 82.5 |
| 300-400 | 170 | 3.0 | 90 | 82.8 |
| 400-500 | 170 | 3.0 | 88 | 82.6 |
| 500-600 | 170 | 3.0 | 96 | 82.6 |
| 600-700 | 170 | 3.0 | 93 | 82.4 |
| 700-816 | 170 | 3.0 | 99 | 82.3 |
| 824-1000 | 170 | 2.0 | 80 | 82.5 |
| 1000-1500 | 170 | 2.0 | 82 | 82.7 |
| 1500-2000 | 170 | 2.0 | 77 | 82.6 |
| 2000-2500 | 170 | 2.0 | 70 | 82.4 |
| 2500-3000 | 170 | 2.0 | 72 | 82.6 |
Claims (11)
1, the application of a kind of selective hydrogenation and olefin hydrocarbon removal catalyzer in the recapitalization generating oil hydrogenation deolefination, described selective hydrogenation and olefin hydrocarbon removal catalyzer is as support of the catalyst with porous, inorganic refractory materials aluminum oxide, have at least a kind ofly to be selected from precious metal in the periodic table of elements group VIII, be selected from least a component in basic metal and the alkaline-earth metal as auxiliary agent as active metal component; The specific surface area of described aluminum oxide is 150～250m
2/ g, pore volume are 0.3～0.8ml/g; It is under the condition that hydrogen exists that this catalyzer is used for the recapitalization generating oil hydrogenation deolefination, described reformed oil is contacted with catalyzer hydrogenation reaction takes place, reaction conditions is: reaction pressure 1.0～3.0MPa, 120～250 ℃ of temperature of reaction, hydrogen to oil volume ratio 100: 1～500: 1, volume space velocity 1～8h during liquid
-1
2, according to the described application of claim 1, it is characterized in that described reaction pressure is 1.2～2.0MPa, temperature of reaction is 150～230 ℃, and hydrogen to oil volume ratio is 200: 1～300: 1, and volume space velocity is 2～4h during liquid
-1
3, according to the described application of claim 1, it is characterized in that in the described selective hydrogenation and olefin hydrocarbon removal catalyzer, precious metal in the described periodic table of elements group VIII is to be selected among Pt and the Pd one or both, and its weight content in catalyzer is 0.1%～1.0%.
4, according to the described application of claim 1, it is characterized in that in the described selective hydrogenation and olefin hydrocarbon removal catalyzer, precious metal in the described periodic table of elements group VIII is to be selected among Pt and the Pd one or both, and its weight content in catalyzer is 0.2%～0.6%.
5, according to the described application of claim 1, it is characterized in that in the described selective hydrogenation and olefin hydrocarbon removal catalyzer that described basic metal and alkaline-earth metal are to be selected among K and Na and the Mg one or more, its weight content in catalyzer is 0.05%～0.5%.
6, according to the described application of claim 1, it is characterized in that in the described selective hydrogenation and olefin hydrocarbon removal catalyzer that described basic metal and alkaline-earth metal are to be selected among K and Na and the Mg one or more, its weight content in catalyzer is 0.1%～0.3%.
7, according to the described application of claim 1, it is characterized in that described selective hydrogenation and olefin hydrocarbon removal Preparation of catalysts method, comprise: described carrier is used the solution that contains described active metal component and adjuvant component, in the presence of competitive adsorbate, flood preparation, catalyzer behind the dipping carries out drying under 110～125 ℃, carry out roasting in 400～500 ℃ airflow, reduces in 150～450 ℃ of hydrogen.
8,, it is characterized in that the described solution that contains active metal component and adjuvant component is salts solution according to the described application of claim 7.
9, according to the described application of claim 7, it is characterized in that described competitive adsorbate is to be selected from mineral acid and the organic acid one or more, be benchmark with butt refractory oxide weight percent, its consumption is 0.1%～1.0%.
10, according to the described application of claim 7, the introducing that it is characterized in that described reactive metal and auxiliary agent is to adopt co-impregnation.
11, according to the application described in the claim 7, the introducing that it is characterized in that described reactive metal and auxiliary agent is to adopt step impregnation method.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109413 CN1282733C (en) | 2002-04-04 | 2002-04-04 | Cytalyst for reformed formation oil selective hydrogen removing olefin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109413 CN1282733C (en) | 2002-04-04 | 2002-04-04 | Cytalyst for reformed formation oil selective hydrogen removing olefin |
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| CN1282733C true CN1282733C (en) | 2006-11-01 |
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| CN104014337B (en) * | 2014-06-10 | 2017-02-01 | 中国科学院山西煤炭化学研究所 | Catalyst for selective hydrogenation and olefin removal of reformed generated oil as well as preparation method and application |
| CN110961124A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenation and olefin removal of reformate, preparation method and application |
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| CN115957804B (en) | 2021-10-13 | 2025-08-01 | 中国石油化工股份有限公司 | Catalyst for effectively converting olefin in aromatic-rich distillate oil, and preparation method and application thereof |
| CN114870890B (en) * | 2022-03-07 | 2024-01-02 | 宁波中金石化有限公司 | Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof |
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| CN117258810A (en) * | 2022-06-15 | 2023-12-22 | 中国石油化工股份有限公司 | Catalyst for removing olefin and oxygen-containing compound, preparation method and hydrofining method |
| CN117625237B (en) * | 2022-08-18 | 2025-07-08 | 中国石油化工股份有限公司 | A reaction device and method for de-olefination reaction of reforming oil and dechlorination and de-olefination |
| CN119060757A (en) * | 2023-06-02 | 2024-12-03 | 中国石油化工股份有限公司 | A method for removing olefins from reformed oil |
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2002
- 2002-04-04 CN CN 02109413 patent/CN1282733C/en not_active Expired - Lifetime
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