CN102408916B - Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation - Google Patents
Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation Download PDFInfo
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- CN102408916B CN102408916B CN201010291710.6A CN201010291710A CN102408916B CN 102408916 B CN102408916 B CN 102408916B CN 201010291710 A CN201010291710 A CN 201010291710A CN 102408916 B CN102408916 B CN 102408916B
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- 238000000034 method Methods 0.000 title claims abstract description 99
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 93
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 27
- 150000001337 aliphatic alkines Chemical class 0.000 title abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 150000001345 alkine derivatives Chemical class 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
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- 150000001298 alcohols Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical compound CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OUHONEIDEVTEIG-UHFFFAOYSA-N ethyl(methoxy)silane Chemical compound CC[SiH2]OC OUHONEIDEVTEIG-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FUMSHFZKHQOOIX-UHFFFAOYSA-N methoxy(tripropyl)silane Chemical compound CCC[Si](CCC)(CCC)OC FUMSHFZKHQOOIX-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 230000001314 paroxysmal effect Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for removing dialkene and alkine from pyrolysis gas through selective hydrogenation, belonging to the hydrogenation field. In order to satisfy the adaptability of catalyst performance to small water content or fluctuant water content in raw material in the selective hydrogenation reaction process of the pyrolysis gas and the inhibition on the generation of carbon deposition, the invention is characterized in that the pyrolysis gas used as the raw material is in contact with a hydrogenation catalyst under the conditions that the temperature is 15-150 DEG C, the pressure is 0.1-5.0 Mpa and the gas hourly space velocity of the pyrolysis gas is 500-20000h<-1>; and alkine and dialkene are changed into alkene through selective hydrogenation, wherein the hydrogenation catalyst contains a carrier, a metal active component palladium and a silane group, and the silane group is subjected to silylation and grafting and has a content of 0.05-25wt%. Compared with the existing method, the method disclosed by the invention ensures that the reaction performance can not be changed obviously when the hydrogenated raw material contains small water content and the reaction performance can be kept basically stable when the hydrogenated raw material contains fluctuant water content; and meanwhile, only a small amount of carbon deposition is generated on the catalyst, thereby ensuring that the catalyst has a longer service life.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly, the present invention relates to a kind of selective hydrogenation of pyrolysis gas and remove the method for alkynes and diolefine.
Background technology
Monoolefine is the important source material in industry, wherein the very important chemical intermediate of ethene, propylene, butylene and vinylbenzene.The mode of commercially producing of alkene has steam cracking, catalytic cracking, thermally splitting, dehydration of alcohols, methanol decomposition reaction and the synthetic alkene of synthetic gas now, and wherein steam cracking is the major way that monoolefine is produced.The ethene that produces in above-mentioned commercial run, propylene, butylene and etc. contain a small amount of alkynes or diolefine in product.Because alkynes and diolefine affect follow-up polyreaction effect and quality product, therefore removing of alkynes and diolefine is the integral part of monoolefine production technology.
Industrial common employing catalysis selective hydrogenation method and solvent extraction method.Because of solvent extraction (claiming again extracting rectifying) method flow complexity, process cost is large, and user is little; Prior art is used selective catalytic hydrogenation method conventionally, and the concentration of alkynes and diolefine is wherein removed to very low level (molar fraction < 1 × 10
-6), to obtain the product of polymerization-grade; Also can increase the output of monoolefine simultaneously, improve resource utilization.
Described splitting gas (Raw Gas) refers in the mode of production of alkene in the present invention, comprise that steam cracking, catalytic cracking, thermally splitting, methanol decomposition reaction and synthetic gas directly synthesize the primary products that are rich in alkene in olefin process, comprise multiple components such as methane, carbon monoxide, hydrogen, ethene, propylene, butylene; More specifically, the splitting gas in steam cracking process is that the gas mixture obtaining through pyrolyzer obtains through processes such as oil wash, washing, compression, alkali cleanings; Splitting gas in methanol decomposition reaction is the gas mixture that methanol decomposition reactor obtains, and for obtaining better effect, also can obtain through overdraft and drying process.
Splitting gas contains multiple components, for obtaining the alkene of polymerization-grade or chemical grade, all needs multiple sepn processes, and catalysis selective hydrogenation comprises selective hydrogenation of pyrolysis gas, " front-end hydrogenation " and " back end hydrogenation " three kinds of techniques thus.Described " front-end hydrogenation " and " back end hydrogenation " refer to that alkyne hydrogenation reactor is for demethanizing tower position, and hydrogenator is front-end hydrogenation before being positioned at demethanizing tower, and hydrogenator is back end hydrogenation after being positioned at demethanizing tower.
Back end hydrogenation except alkynes be to join quantitatively respectively in deethanizing tower top material by demethanizing tower top material (methane, hydrogen and carbon monoxide) and by the material (methane and hydrogen) that methanator has been removed carbon monoxide, by selecting hydrogenation and removing alkynes wherein.Reaction pressure and carbon monoxide concentration are larger on catalyst performance impact, and the amount that needs careful control to add hydrogen and CO during therefore except acetylene regulates the selectivity of carbon two hydrogenation catalysts.In addition, while being subject to the impact of hydrogen importing impurity (as CO, methane etc.) due to the purity of ethylene product, there are fluctuation, downstream ethylene column need establish " bar formula rectifying section ", or the second demethanizing tower are set to separate remaining hydrogen and methane.
Front-end hydrogenation technology has front-end deethanization front-end hydrogenation and two kinds of techniques of predepropanization front-end hydrogenation.Front-end deethanization front-end hydrogenation technique is front-end deethanization tower top material (methane, hydrogen, carbon monoxide and carbon two fractions) to be passed through before entering demethanizing tower select hydrogenation and removing acetylene wherein.The palladium catalyst containing promotor of the characteristics such as to have ethylene selectivity high owing to successfully developing, and green oil generating amount is little, large air speed, front-end hydrogenation is adopted by increasing ethylene unit except alkynes technology.Predepropanization front-end hydrogenation technique is by predepropanization tower top material (methane, hydrogen, carbon monoxide, C
2fraction and C
3fraction) before entering demethanizing tower by selecting wherein acetylene and part propine, propadiene of hydrogenation and removing.
The shortcoming of front-end hydrogenation technology is owing to containing a large amount of hydrogen and carbon monoxide content fluctuation in material, cause reactor outlet easily to leak alkynes or operate abnormal phenomenon, these abnormalities are because go into operation susceptibility and the active temperature excursion causing of initial stage live catalyst of ethylene unit produces.In addition, hydrogen is to separate in the higher demethanizing tower system of energy consumption with methane, so it is higher to enter the hydrogen content of demethanizing tower, energy consumption is higher.
Splitting gas mixed phase hydrogenation refers to from the splitting gas of the pyrolyzer of steam cracking through processes such as oil wash, washing, compression, alkali cleanings, before drying tower or after by mixed phase by middle high unsaturated hydrocarbons hydrogenation and removing.The advantage of employing selective hydrogenation of pyrolysis gas technique is to reduce the quantity of hydrogenation unit, the amounts of hydrogen that minimizing enters cryogenic unit, the content that reduces diolefine in predepropanization or front-end deethanization, raising ethene and propene yield, significantly reduces separating energy consumption, minimizing tower reactor coking amount, saving facility investment and production cost thereby reach.
Chinese patent CN 1109090C has proposed the method for carbon two～carbon ten high unsaturated hydrocarbons (alkynes and diolefine) being carried out to selective hydrogenation at predepropanization tower or front-end deethanization tower upstream side.Make to enter mixed phase hydrogenator from the cleavage product stream of alkene and select hydrogenation, then enter predepropanization tower or front-end deethanization tower, a liquid phase stream part for tower reactor loops back mixed phase hydrogenator and rinses beds as liquid phase stream.This patented technology can reduce the reaction unit number of alkynes complete hydrogenation, reduce the hydrogen content that enters predepropanization tower or front-end deethanization tower, deep cooling part, reduce energy consumption and equipment size, also can reduce the diolefin content that enters predepropanization tower or front ethane tower, reduce tower reactor coking amount and reduce energy consumption.
U.S. Pat 5059732 proposes a kind of splitting gas mixed phase hydrogenation technique, this technique is by dried splitting gas (gas phase) and hydrogenation is saturated pyrolysis gasoline (liquid phase, when driving, replace with toluene) be mixed in shell and tube hydrogenator, after reactor outlet logistics is cooling, send into knockout tower.Top gaseous phase logistics contains hydrogen and carbon one, carbon two, carbon three and C-4-fraction, send into downstream separation device, tower reactor liquid phase stream contains carbon five to C 9 fraction (pyrolysis gasoline) and a small amount of carbon four, a part is circulated in mixed phase hydrogenator, and rest part is as pyrolysis gasoline or aromatic device raw material.Pyrolysis gasoline can, by rinsing the colloid of the deposition on catalyzer, can be removed exothermic heat of reaction simultaneously in time.
Splitting gas composition is except containing hydrogen, methane, C
2fraction and C
3outside fraction, also contain take divinyl as main C
4fraction and a small amount of C
5diolefin, because the polymkeric substance generating due to diene polymerization when the catalysis selective hydrogenation makes catalyst deactivation very fast, becomes the important restriction of splitting gas mixed phase hydrogenation.As everyone knows, the life-span of catalyzer improves efficiency, energy consumption and the economic benefit of raising reaction unit most important.In certain temperature of reaction, outside the easy polymerization of diolefine, also may with logistics in other alkene react, the coking presomas such as production colloid, cause the surperficial hydrogenation activity position of catalyzer capped, reduce catalyst activity; Also can stop up duct simultaneously, reduce the spread coefficient of catalyzer, further reduce the reactivity worth (F.Schuth of catalyzer, J.Weitkamp, Handbook of heterogeneous catalysis:Second Edition, 2008, P3266-3308.).Therefore,, for the inactivation of hydrogenation of unsaturated hydrocarbons catalyzer, carbon distribution is usually extremely important or major cause.For high unsaturated hydrocarbons selective hydrogenation catalyst, the existence of carbon distribution also can reduce selectivity.
For suppressing the inactivation of catalyzer, the liquid phases such as pyrolysis gasoline, the intersegmental compression liquid in compression section are often used to rinse beds, but these usually inevitably can exist a certain amount of water in rinsing mutually.Simultaneously, water-content lower (general dew point is lower than-70 ℃) in splitting gas after drying tower, but in industrial operation, the moisture eliminator drainage that unpredictable accident likely occurs, especially in drying tower possibility increase of leaking during with switching for subsequent use and existing.Contain a certain amount of water vapour for the splitting gas before dry, generally at 0.01wt%-1wt%.For used metal hydrogenation catalyzer, the existence of water will significantly reduce the hydrogenation activity of catalyzer, and water even can reduce the work-ing life of catalyzer; Paroxysmal water-content fluctuation also can cause the Hydrogenation fluctuation of catalyzer, makes the unstable of whole splitting gas tripping device operation, and this difficulty that has increased undoubtedly operator has also reduced the security of process.
In sum, remove in alkynes and diolefine at selective hydrogenation of pyrolysis gas, overcome the moisture or water-content of raw material and fluctuate to catalyst reaction performance impact, suppress safe, steadily and high-efficiency operation important in inhibiting to olefin production plant of catalyst carbon deposition growing amount simultaneously.
Summary of the invention
For meeting the adaptability that in selective hydrogenation of pyrolysis gas reaction process, catalyst performance contains water or water-content fluctuation to raw material and the two aspect requirements that generate suppressing carbon distribution, the present invention proposes a kind of method, can effectively solve moisture in splitting gas raw material or the water-content problem that catalyst hydrogenation performance is impacted that fluctuates, method of the present invention can also suppress the growing amount of carbon distribution on catalyzer simultaneously.
The present invention relates to a kind of method that selective hydrogenation of pyrolysis gas removes alkynes and diolefine, particularly, method of the present invention is take splitting gas as raw material, 15 ℃～150 ℃ of temperature of reaction, reaction pressure 0.1MPa～5.0MPa, splitting gas gas hourly space velocity 500h
-1～20000h
-1splitting gas contacts with hydrogenation catalyst, alkynes in splitting gas and diolefin hydrogenate are alkene, it is characterized by catalyzer and contain carrier, be carried on metal active constituent palladium and silane group on carrier, and silane group on described catalyzer is processed grafting through silylanizing.With respect to existing method, method of the present invention has the two obvious advantages in aspect: the transformation efficiency of alkynes and diolefine and selectivity are subject to the impact of water-content and water-content fluctuation in raw material less; Catalyst surface carbon distribution growing amount is little, the long service life of catalyzer.
The present inventor finds by utilizing silane group in grafting can change adsorptive capacity and the adsorption strength of water on catalyzer on the carrier supported catalyst that contains hydroxyl through deep research, also find the silane group of grafting simultaneously after water molecules adsorptive capacity on metal active position significantly reduce.The inventor finds that it is the surface hydroxyl quantity of catalyzer that carbon distribution has very close relationship, although also there is no strict proof at present, but contriver thinks that after theory is inferred the reactive hydrogen on the surface hydroxyl of catalyzer has promoter action for the unsaturated link(age) polymerization in hydro carbons, and the reactive hydrogen quantity on methyl-monosilane rear catalyst surface significantly reduces.The present invention completes based on above discovery.
Concrete technical scheme is as follows:
Selective hydrogenation of pyrolysis gas of the present invention removes the method for alkynes and diolefine, is take splitting gas as raw material, at reaction 15 ℃～150 ℃ of temperature ins, reaction pressure 0.1MPa～5.0MPa and splitting gas gas hourly space velocity 500h
-1～20000h
-1under, splitting gas is contacted with hydrogenation catalyst, the alkynes in splitting gas and diolefin hydrogenate are alkene, described hydrogenation catalyst contains carrier, metal active constituent palladium and silane group, and silane group is processed grafting through silylanizing.
In described hydrogenation catalyst, the percentage ratio that described metal active constituent palladium accounts for catalyzer gross weight is preferably 0.005wt%～2wt%, more preferably 0.01wt%～1wt%, more preferably 0.05wt%～0.5wt%.
In order to improve the catalytic performance of catalyzer, in above-mentioned various catalyzer schemes, described catalyzer preferably also contains metal promoter a, described metal promoter a is more than one the metallic element in IA family, IIA family, IIIA family, IVA and VA family, and its content is the 0.01wt%～10wt% of catalyzer gross weight.Preferably described metal promoter a comprises more than one metallic element of sodium, potassium, caesium, calcium, magnesium, barium, Gallium, indium, lead and bismuth, and its content is the 0.01wt%～6wt% of catalyzer gross weight.
In order to improve the catalytic performance of catalyzer, in the above-mentioned various catalyzer schemes that do not contain metal promoter a and contain metal promoter a, described catalyzer also contains metal promoter b, described metal promoter b is more than one metallic element in IB family, IIB family, IIIB family and group vib, and its content is the 0.01wt%～10wt% of catalyzer gross weight.Preferably, described metal promoter b comprises more than one the metallic element in copper, silver, gold, zinc, mercury, lanthanum, thorium, cerium, chromium, molybdenum and tungsten, and its content is the 0.05wt%～6wt% of catalyzer gross weight.
In order further to improve the catalytic performance of catalyzer, above-mentionedly not containing metal promoter a and b, only contain metal promoter a, only contain metal promoter b and contain in the various catalyzer schemes of metal promoter a and b simultaneously, described catalyzer also contains non-metal assistant d, described non-metal assistant d is more than one non-metallic element in IIIA family, IVA and VA family, and its content is the 0.01wt%～8wt% of catalyzer gross weight.Preferably, described non-metal assistant d comprises in boron, phosphorus, sulphur, selenium, fluorine, chlorine and iodine more than one non-metallic element, and its content is the 0.01wt%～4wt% of catalyzer gross weight.
Catalyzer of the present invention can use any carrier, but from the industrial application situation of hydrogenation of unsaturated hydrocarbons, preferably described carrier is selected from Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2, ZrO
2, one or more mixture in MgO, gac, kaolin and diatomite, or carrier is by Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2with in MgO, at least one is carried on the complex carrier forming on inertial base, described inertial base comprises metal base and pottery.More preferably, described carrier is Al
2o
3, TiO
2, ZrO
2, one or more mixture in ZnO, MgO, gac and diatomite.Mixture in the present invention not only can their mechanical mixture, can be also the mixed oxide that has chemical bond to exist, as Al
2o
3-SiO
2.
In catalyzer of the present invention, described silane group is processed grafting through silylanizing, more preferably described silane group by silylanizing method take silicomethane base as raw material grafting, account for the 0.05wt%～25wt% of catalyzer gross weight, preferred described silane group accounts for the 0.1wt%～15wt% of catalyzer gross weight.
In silylanizing process, described silicomethane base is a kind of in organosilane, organo-siloxane, organosilazanes and organic oxosilane or two or more mixture in them preferably, more preferably a kind of in organo-siloxane and organosilazanes or their mixture.
Preferably, described splitting gas is the one or more kinds of mixtures in the splitting gas generating in steam cracking, catalytic pyrolysis, catalytic cracking or methanol decomposition olefin process processed.More preferably, described splitting gas is the mixture of a kind of in the splitting gas generating in steam cracking or methanol decomposition alkene synthesis technique processed or two kinds.
For the life-span of extending catalyst with reaction heat is shifted out in time, in splitting gas hydrogenator, also introduce the flushing phase of one liquid phase stream as beds, described liquid phase stream is the one or more kinds of mixtures in the mixed solution of toluene, dimethylbenzene, the intersegmental cooling fluid in compression section, depropanizing tower tower reactor still liquid, debutanizing tower tower reactor still liquid, depentanizer tower reactor still liquid, pyrolysis gasoline, carbon five raffinate hydrogenation mixed solution, carbon nine hydrogenation saturated solutions and the aromatic hydrocarbons raffinate hydrogenation after saturated after saturated.Preferably, volume space velocity is 0.1h when the liquid of described liquid phase stream
-1～20h
-1.
As the composition of the hydrogenation catalyst in the present invention, except silane group part, be exemplified below: Pd/Al
2o
3, Pd-Ag/Al
2o
3, Pd-Ag-K/Al
2o
3, Pd/MgAl
2o
4, Pd-Ag/SiO
2, Pd/ gac, Cu/SiO
2, Cu/ZnO-Al
2o
3, Ni-Ca/Al
2o
3, Pd-Ca/Al
2o
3, Ni/Al
2o
3, Ni-Co/Al
2o
3, Ni/ diatomite, Ni-Mo-S/Al
2o
3, Ni/ZrO
2-TiO
2, Pt-K/Al
2o
3, Ru-Sn/Al
2o
3, Ru/ gac, Ru/SiO
2.
Although silane group still imperfectly understands in the grafting situation of catalyst surface,, can make rational supposition to the form of silane group according to the principle of the molecular structure of silylating reagent and Silanization reaction.Several silane groups existence form after grafting on catalyzer of below giving an example wherein:
Described silane group can be explained with following general formula (1):
Wherein, substituent R
1, R
2and R
3can be identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Described silane group can also be explained with following general formula (2):
Wherein substituent R
1, R
2, R
4and R
5can be identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., according to the option demand of reaction, alkyl can also be aromatic, substituent R simultaneously
3be the one in chlorine, nitrogen and oxygen, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Described silane group can also be explained with following general formula (3):
Wherein substituent R
1and R
2can be identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
The mode that metal component loads on carrier can be multiple, for example, flood by the salt of metallic element or the solution of oxide compound or suspension, then dry.Dry post-heating to 300 ℃～600 ℃ of roastings are metal oxide, and the atmosphere of roasting can be air, nitrogen, oxygen, argon gas or their mixture.The another kind of method of metal component load is that the salt of metallic element or the solution of oxide compound or suspension flood, then dry, can also use a kind of reductive agent after dry metal component is converted into zero-valent metal state in whole or in part.The reductive agent using comprises hydrogen, hydrogeneous gas, polyvalent alcohol or hydrazine, gas and the polyvalent alcohol of handy hydrogen, and reductive agent can be reduced to active metallic compound on corresponding metal or compared with the compound of suboxide valency.In addition, metal component also can load on carrier by the mode of spraying, metal or metallorganics evaporation, uniform deposition.Above to metal component carrying method be for example just metal component load on explanation catalyzer, those skilled in the art can be easily by conversion step to realize the load of metal component and adding of auxiliary agent, these do not affect essence of the present invention.
Auxiliary agent can load on carrier to realize the Hydrogenation that improves catalyzer by the above-mentioned carrying method identical with metal component.The joining day of auxiliary agent can be before active metal load, add afterwards or together with active metal.Adding of auxiliary agent can also be in the moulding process of carrier.In the moulding process of carrier, the salt of metal promoter or oxide compound can add, and are dispersed on catalyzer.
Because silylating reagent has higher reactive behavior, therefore the concrete reaction in silanization treating processes is not still come to a conclusion completely.Apply in chromatogram according to Silanization reaction obtain empirical principle, in silylation treating processes, silane group by silylanizing method, the hydroxyl on silicomethane base and catalyst surface is carried out to condensation reaction and grafting to catalyst surface.Be exemplified below take organo-siloxane as the principle of silicomethane base raw material:
Grafting process can be carried out in liquid phase solvent, and effectively solvent can be a kind of in ketone, ether, hydrocarbon and ester, preferably ether and hydro carbons.Particularly, effectively solvent can be one or the mixed solvent in toluene, benzene, dimethylbenzene, hexanaphthene, normal hexane, heptane, ether, methyl-phenoxide, tetrahydrofuran (THF), whiteruss, the saturated gasoline of hydrogenation, the saturated diesel oil of hydrogenation, sherwood oil.Grafting process generally need to be controlled temperature at 30 ℃～320 ℃, is preferably 50 ℃～180 ℃.
The grafting of silane group also can be by another kind of way: silicomethane base form with gas or fine droplet under the carrying of carrier gas is contacted with catalyzer, thereby complete the silylation processing to catalyzer.The carrier gas using can be a kind of in nitrogen, air, hydrogen, oxygen, carbonic acid gas and argon gas or two or more mixture in them.In the limited Catalyst Production factory of some conditions, in absence lower time of carrier gas, contacts the grafting of carrying out silane group after also silicomethane base can being heated to be to steam with catalyzer.When grafting, temperature is controlled at 60 ℃～450 ℃, preferably at 85 ℃～280 ℃ by this method.
Silicomethane base can be selected from organosilane, organo-siloxane, at least one in organosilazanes and organic oxosilane, for example, for example Union carbide A-162, dimethyldiethoxysilane, trimethylammonium diethoxy silane, ethyl triethoxysilane, diethyl diethoxy silane, triethyl-ethoxy-silicane alkane, ethyl trimethoxy silane, butyl triethoxyl silane, dimethyl one ethyl methoxy silane, dimethyl one phenyl ethoxy silane, tripropyl methoxy silane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), dimethyl one propyl chloride silane, dimethylbutyl chlorosilane, dimethyl isopropyl chloride silane, tributyl chlorosilane, hexamethyldisilazane, heptamethyldisilazane, tetramethyl-disilazane, 1, 3-dimethyl diethyl disilazane, 1, 3-phenylbenzene tetramethyl-disilazane etc.
Silane group is very large to catalyzer water resisting property of the present invention and anti-carbon performance impact in the coverage of catalyst surface.In the time that coverage is low, water resisting property and anti-carbon performance can not be brought into play completely, and in the time that coverage is too high, thereby may cause the Adsorption of polymerization covering catalyst between silane, reduce the activity of catalyzer, therefore need to control the content of silane group in catalyzer, generally account for catalyzer total mass 0.05wt%～25wt%, be preferably 0.1wt%～15wt%.The coverage of silane group can be by regulating the methods such as silicomethane base raw material, silylanizing treatment time, silylanizing treatment temp, carrier gas kind and flow velocity (vapor phase process) and solvent (liquid phase method) to realize point-device control.In the time using gas phase silylanizing, silicomethane base raw material at beds residence time general control at 0.001 second～400 seconds.The vapor phase process overall operation time, saving running cost and operating time can also regulate silicomethane base material concentration to realize at 1 minute～80 hours.And in the time using liquid phase method, the scope control of the time residence time was at 0.5 second～24 hours.
On hydrogenation catalyst of the present invention, the coverage of the silane group of grafting can, by using x-ray photoelectron power spectrum (XPS) to analyze, be confirmed the amount of carbon atom of catalyst surface, thus gauging surface coverage; Also can use infrared instrument (IR) to observe the functional group of catalyst surface, as pass through-CH
3characteristic peak (～2970cm
-1) gauging surface silane level of coverage, the characteristic peak (～3750cm of pass through-OH
-1) calculate catalyst surface hydroxyl residual content.Can be by organic carbon/elemental carbon (OC/EC) thus the quantitative organic carbon content of analyser accurately obtains the silylation quality on catalyzer.
As everyone knows, hydrogenation catalyst generally need to carry out pre-treatment before use.Described in method of the present invention, catalyzer needs pre-treatment before use, and pre-treatment is to be mainly corresponding active state or by the impurity removal adsorbing on catalyzer by catalyst reduction.Reduction pretreatment can adopt hydrogen, hydrogen-containing gas, CO or hydrazine metal oxide on catalyzer to be reduced to the metal of zeroth order or lower valency.Above-described these pre-treatment are all known as the professionals.
Method of the present invention is to be applied to the reaction member that diolefine in the splitting gas producing in the alkene synthesis techniques such as steam cracking, catalytic cracking and methanol decomposition and selective acetylene hydrocarbon hydrogenation are monoolefine.Preferably, method of the present invention is the reaction member that in a kind of in the splitting gas for generating in steam cracking and methanol decomposition alkene synthesis technique or two kinds, diolefine and selective acetylene hydrocarbon hydrogenation are monoolefine.Method of the present invention is more preferably applied to diolefine in the splitting gas that steam cracking produces and the selective acetylene hydrocarbon hydrogenation reaction member that is monoolefine.The splitting gas that described steam cracking produces can be the mixing gas phase flowing out before drying tower or after drying tower, can also be the mixing gas phase that the compressor after drying tower flows out.The gas hourly space velocity of splitting gas described in the present invention 500h
-1-20000h
-1, be preferably controlled at 3000h
-1-12000h
-1.
Method of the present invention is applicable to gas-liquid phase-solid phase three-phase system or gas phase-solid phase two-phase system.Particularly, in the removing of splitting gas, splitting gas gas phase can be carried out on catalyzer of the present invention to hydrogenation reaction, form described gas phase-solid phase two-phase system.Meanwhile, according to factory reactor heat is shifted out or the requirement of catalyzer single pass life, can also introduce the flushing phase of one liquid phase as hydrogenator, form gas-liquid phase-solid phase three-phase reaction system with splitting gas and hydrogenation catalyst thus.In splitting gas hydrogenator, can also introduce the flushing phase of one liquid phase as beds.Described liquid phase is the one or more kinds of mixtures of the mixed solution of toluene, dimethylbenzene, the intersegmental cooling fluid in compression section, depropanizing tower tower reactor still liquid, debutanizing tower tower reactor still liquid, depentanizer tower reactor still liquid, pyrolysis gasoline, carbon five raffinate hydrogenation mixed solution, carbon nine hydrogenation saturated solutions, the aromatic hydrocarbons raffinate hydrogenation after saturated after saturated.The liquid hourly space velocity of described liquid phase is controlled at 0.1h
-1-10.0h
-1.
In the type of reactor, method of the present invention can be used any one in fixed bed, fluidized-bed, slurry state bed, moving-bed, Magnetic suspension float bed, reaction rectification bed.The combination that changes the type of reactor or form between different reactor does not change the essence that the present invention invents.For the technician of this professional domain, can adjust according to the needs of different production plants.
Method of the present invention can, for the selective hydrogenation of pyrolysis gas in catalyzed reaction-rectifying reactor, be that catalyzer can be seated in arbitrary position of tower body, is preferably seated in rectifying section in the filling of catalyzer.
The reaction conditions of splitting gas hydrogenator need to be controlled, and the control of temperature of reaction generally refers to the temperature in of controlling reactor, and reactor inlet temperature is controlled at 15 ℃～150 ℃ in the method for the invention, preferably at 30 ℃～90 ℃.Splitting gas reactor pressure 0.1MPa～5.0MPa in the inventive method.The stable control of reaction pressure and reactor inlet is by current professional and technical personnel is known.
Method of the present invention, being applied in hydrogenation of unsaturated hydrocarbons process, is limited to 25wt% in the water content in permission raw material.Certainly, in higher water content situation, for splitting gas liquid-phase hydrogenatin technique, water with splitting gas raw material in liquid phase have obvious demixing phenomenon, in actual industrial operation, generally can first carry out multi_layer extraction operation.
Remove alkynes and diolefine technology with respect to existing selective hydrogenation of pyrolysis gas, selective hydrogenation of pyrolysis gas method of hydrotreating of the present invention has the following advantages:
(1) aspect of the present invention has obvious adaptability to raw materials.The in the situation that in raw material, water-content being higher, the reactivity worth of catalyzer changes very little with respect to the water-free situation of raw material; Special in raw material pulse enter in a certain amount of water or raw material in the situation that water-content having larger fluctuation, can there are not big ups and downs in the reactivity worth of catalyzer.This safe and stable operation to device has larger help.
(2) method of the present invention can suppress the generation of polymkeric substance on catalyzer significantly, thereby reduces the carbon distribution generating in reaction, the work-ing life of significantly improving catalyzer;
(3) catalyzer that method of the present invention is used can partly utilize prior art and equipment, and industry is amplified simple, and the relatively existing method of cost increases less;
Embodiment
Following examples are to more detailed the describing for example of the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
The spherical Pd-Au-Ca/Al of tooth of cut-off footpath 2.0mm
2o
315 grams of catalyzer (Beijing Chemical Research Institute produces, volume 35ml, and the mass percentage content of Pd, Au, Ca is respectively 0.1%, 0.1%, 0.5%, and surplus is Al
2o
3, the weightless 1.2wt% of catalyzer when temperature rises to 500 ℃ on thermogravimetric analyzer), catalyzer is packed in fixed-bed reactor (diameter 15mm, length 400mm are with two temperature to show reference mark).Be stabilized in after 110 ℃ at temperature of reactor, the nitrogen of the trimethylammonium methoxy silane containing 2vol% is passed in reactor, flow control is at 150ml/min, 110 ℃ are warming up to 150 ℃ after maintaining 1 hour, after temperature-stable, keep within 0.5 hour, stopping entering the nitrogen containing trimethylammonium methoxy silane, fill into argon gas cooling, obtain catalyzer Cat-1.
By relatively Pd-Au-Ca/Al of Fourier's infrared spectrometric analyzer (FTIR)
2o
3and Cat-1, the characteristic peak (～2970cm of the methyl on Cat-1
-1) be obviously better than Pd-Au-Ca/Al
2o
3, and the characteristic peak (～3750cm of hydroxyl
-1) be obviously weaker than Pd-Au-Ca/Al
2o
3, this illustrates Pd-Au-Ca/Al
2o
3on part of hydroxyl replaced by silylation.ICP-AES elemental analyser is analyzed Si content, and in quantitatively rear Cat-1, Si content is 1.0wt%; Be 1.41wt% by the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser, the silylation mass percent on catalyzer is 3.20wt% accordingly simultaneously.
Comparative example 1
The spherical Pd-Au-Ca/Al of tooth of cut-off footpath 2.0mm
2o
315 grams of catalyzer (Beijing Chemical Research Institute produces, identical with embodiment 1), pack catalyzer in one fixed-bed reactor (diameter 15mm, length 400mm are with two temperature to show reference mark) into.Be stabilized in after 110 ℃ at temperature of reactor, nitrogen is passed in reactor, flow control is at 150ml/min, and 110 ℃ are warming up to 150 ℃ after maintaining 1 hour, keep stopping entering nitrogen in 0.5 hour after temperature-stable, fill into argon gas cooling, obtain catalyzer Cat-2.
By relatively Pd-Pb-Bi/Al of Fourier's infrared spectrometric analyzer (FTIR)
2o
3and Cat-2, Cat-2 and Pd-Pb-Bi/Al
2o
3on equal to obvious methyl characteristic peak (～2970cm
-1), and the characteristic peak (～3750cm of hydroxyl
-1) be slightly weaker than Pd-Ag/Al
2o
3.ICP-AES elemental analyser is analyzed Si content, and in quantitatively rear Cat-2, Si content is 0.001wt%; Pass through the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser lower than instrument lower limit simultaneously.
Embodiment 2
The spherical Pd-F-Cu-K/SiO of cut-off footpath 3mm
225 grams of catalyzer (Beijing Chemical Research Institute produces, volume 53ml, and the mass percentage content of Pd, F, Cu and K is respectively 0.08%, 0.4%, 1.0% and 0.5%, and surplus is SiO
2, weightless 1.1wt% when temperature rises to 500 ℃ on thermogravimetric analyzer), catalyzer is packed in a 500ml there-necked flask, there-necked flask is placed in oil bath, and a bite in there-necked flask connects cooling coil, and a bite jointing temp meter connects opening for feed flatly.First in there-necked flask, pour 150ml p-Xylol into, and will be stabilized in after 110 ℃ at temperature of reactor, by passing in reactor of the trimethylchlorosilane containing 8ml.110 ℃ are warming up to 140 ℃ after maintaining 1h, keep cooling after 1 hour after temperature-stable, take out catalyzer 160 ℃ of dry 3h in baking oven, obtain catalyzer Cat-3.
By relatively Pd-F-Cu-K/SiO of Fourier's infrared spectrometric analyzer (FTIR)
2and Cat-3, the characteristic peak (～2970cm of the methyl on Cat-3
-1) be obviously better than Pd-F-Cu-K/SiO
2, and the characteristic peak (～3750cm of hydroxyl
-1) be obviously weaker than Pd-F-Cu-K/SiO
2-Al
2o
3, this illustrates Pd-F-Cu-K/SiO
2on part of hydroxyl replaced by silylation.Be 1.10wt% by the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser, the silylation mass percent on catalyzer is about 2.55wt% accordingly.
Comparative example 2
The spherical Pd-F-Cu-K/SiO of cut-off footpath 3mm
225 grams of catalyzer (Beijing Chemical Research Institute produces, and volume 53ml is identical with embodiment 2), catalyzer is packed in a 500ml there-necked flask, and there-necked flask is placed in oil bath, and a bite in there-necked flask connects cooling coil, a bite jointing temp meter, connects opening for feed flatly.First in there-necked flask, pour 150ml p-Xylol into, and will be stabilized in after 110 ℃ at temperature of reactor, by passing in reactor of the trimethylchlorosilane containing 8ml.110 ℃ are warming up to 140 ℃ after maintaining 1h, keep cooling after 1 hour after temperature-stable, take out catalyzer 160 ℃ of dry 3h in baking oven, obtain catalyzer Cat-4.
By relatively Pd-F-Cu-K/SiO of Fourier's infrared spectrometric analyzer (FTIR)
2and Cat-4, Cat-4 and Pd-F-Cu-K/SiO
2on the characteristic peak (～2970cm of the methyl that all do not have
-1), and the characteristic peak (～3750cm of hydroxyl
-1) and Pd-F-Cu-K/SiO
2close.Be 0.02wt% by the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser.
Embodiment 3
The catalyzer of embodiment 1 and comparative example 1 is applied to respectively to splitting gas mixed phase hydrogenation reaction, and wherein raw cracked gas derives from Sinopec Yanshan Petrochemical company, is taken at five sections of compressor outlets, forms as shown in table 1.
Table 1 splitting gas composition (mol%)
Mixed phase hydrogenator is take pyrolysis gasoline as rinsing phase, liquid air speed 5h
-1, wherein pyrolysis gasoline is hydrogenation after saturated, 82 ℃～178 ℃ of boiling points, water content 500ppm (mol).
Hydrogenator is 15ml isothermal fixed bed, catalyzer 5.0g.The processing condition of hydrogenation reaction are as table 2.In hydrogenation reaction, enter the water vapour of 1ml in 100h pulse to investigate the water resistant fluctuation of catalyzer.After finishing, reaction 700h compares carbon deposition quantity by TG-MS combination.
Result is as shown in table 2, and experiment shows with respect to existing method, method of the present invention in raw material in moisture situation catalyst activity higher, to unexpected water-content, fluctuation has higher adaptive faculty simultaneously, and catalyzer carbon accumulation resisting ability strengthens.
The catalyst reactivity worth of table 2 embodiment 1 and comparative example 1
Carbon deposition quantity is measured: TG-MS combination instrument, in the air atmosphere of 30ml/min, 10 ℃/Min of temperature rise rate, from room temperature to 450 ℃ and maintain 1 hour, according to CO in mass spectrum
2the weightless peak position of thermogravimetric carbon distribution quantitative according to the weightless result of thermogravimetric is determined at peak.
Embodiment 4
The catalyzer of embodiment 2 and comparative example 2 is applied to respectively to splitting gas mixed phase hydrogenation reaction, and wherein raw cracked gas derives from Sinopec east petro-chemical corporation, after being taken at depickling gas tower and before drying tower, forms as shown in table 3.
Table 3 splitting gas composition (mol%)
Mixed phase hydrogenation does not adopt flushing phase, but splitting gas gas phase hydrogenation.Hydrogenator is insulation fix bed.After finishing, reaction 300h compares carbon deposition quantity by TG-MS combination.
Result is as shown in table 4, tests and shows with respect to existing method, and the hydrogenation efficiency of method of the present invention reaction unit in the time of water-containing material is high, and on catalyzer, carbon distribution growing amount is little simultaneously, has higher catalyst stability.
The catalyst reactivity worth of table 4 embodiment 2 and comparative example 2
Carbon deposition quantity is measured: TG-MS combination instrument, in the air atmosphere of 30ml/min, 10 ℃/Min of temperature rise rate, from room temperature to 450 ℃ and maintain 1 hour, according to CO in mass spectrum
2the weightless peak position of thermogravimetric carbon distribution quantitative according to the weightless result of thermogravimetric is determined at peak.
Claims (20)
1. selective hydrogenation of pyrolysis gas removes a method for alkynes and diolefine, it is characterized in that, take splitting gas as raw material, at reaction 15 ℃～150 ℃ of temperature ins, reaction pressure 0.1MPa～5.0MPa and splitting gas gas hourly space velocity 500h
-1～20000h
-1under, splitting gas is contacted with hydrogenation catalyst, alkynes in splitting gas and diolefin hydrogenate are alkene, described hydrogenation catalyst contains carrier, metal active constituent palladium and silane group, and silane group is processed grafting through silylanizing after described carrier to load metal active component palladium.
2. the method for claim 1, is characterized in that, the percentage ratio that described metal active group palladium accounts for catalyzer gross weight is 0.005wt%～2wt%.
3. method as claimed in claim 2, is characterized in that, the percentage ratio that described metal active group palladium accounts for catalyzer gross weight is 0.01wt%～1wt%.
4. method as claimed in claim 3, is characterized in that, the percentage ratio that described metal active group palladium accounts for catalyzer gross weight is 0.05wt%～0.5wt%.
5. the method for claim 1, it is characterized in that, described catalyzer also contains metal promoter a, and described metal promoter a is more than one the metallic element in IA family, IIA family, IIIA family, IVA and VA family, and its content is the 0.01wt%～10wt% of catalyzer gross weight.
6. method as claimed in claim 5, is characterized in that, described metal promoter a comprises more than one metallic element of sodium, potassium, caesium, calcium, magnesium, barium, Gallium, indium, lead and bismuth, and its content is the 0.01wt%～6wt% of catalyzer gross weight.
7. the method as described in claim 1 or 5, it is characterized in that, described catalyzer also contains metal promoter b, and described metal promoter b is more than one metallic element in IB family, IIB family, IIIB family and group vib, and its content is the 0.01wt%～10wt% of catalyzer gross weight.
8. method as claimed in claim 7, is characterized in that, described metal promoter b comprises more than one the metallic element in copper, silver, gold, zinc, mercury, lanthanum, thorium, cerium, chromium, molybdenum and tungsten, and its content is the 0.05wt%～6wt% of catalyzer gross weight.
9. the method as described in claim 1 or 5, it is characterized in that, described catalyzer also contains non-metal assistant d, and described non-metal assistant d is more than one non-metallic element in IIIA family, IVA and VA family, and its content is the 0.01wt%～8wt% of catalyzer gross weight.
10. the method as described in claim 1 or 5, it is characterized in that, described catalyzer also contains non-metal assistant d, and described non-metal assistant d comprises in boron, phosphorus, sulphur, selenium, fluorine, chlorine and iodine more than one non-metallic element, and its content is the 0.01wt%～4wt% of catalyzer gross weight.
11. the method for claim 1, is characterized in that, described carrier is selected from Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2, ZrO
2, one or more mixture in MgO, gac, kaolin and diatomite, or carrier is by Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2with in MgO, at least one is carried on the complex carrier forming on inertial base, described inertial base comprises metal base and pottery.
12. methods as claimed in claim 11, is characterized in that, described carrier is Al
2o
3, TiO
2, ZrO
2, one or more mixture in ZnO, MgO, gac and diatomite.
13. the method for claim 1, is characterized in that, described silane group take silicomethane base as raw material grafting, accounts for the 0.05wt%～25wt% of catalyzer gross weight by silylanizing method.
14. methods as claimed in claim 13, is characterized in that, described silane group accounts for the 0.1wt%～15wt% of catalyzer gross weight.
15. the method for claim 1, is characterized in that, described silicomethane base is a kind of in organosilane, organo-siloxane, organosilazanes and organic oxosilane or two or more mixture in them.
16. methods as claimed in claim 15, is characterized in that, the silicomethane base of use is a kind of in organo-siloxane and organosilazanes or their mixture.
17. the method for claim 1, is characterized in that, described splitting gas is the one or more kinds of mixtures in the splitting gas generating in steam cracking, catalytic pyrolysis, catalytic cracking or methanol decomposition olefin process processed.
18. the method for claim 1, is characterized in that, described splitting gas is the mixture of a kind of in the splitting gas generating in steam cracking or methanol decomposition alkene synthesis technique processed or two kinds.
19. the method for claim 1, it is characterized in that, in splitting gas hydrogenator, also introduce the flushing phase of one liquid phase stream as beds, described liquid phase stream is the one or more kinds of mixtures in the mixed solution of toluene, dimethylbenzene, the intersegmental cooling fluid in compression section, depropanizing tower tower reactor still liquid, debutanizing tower tower reactor still liquid, depentanizer tower reactor still liquid, pyrolysis gasoline, carbon five raffinate hydrogenation mixed solution, carbon nine hydrogenation saturated solutions and the aromatic hydrocarbons raffinate hydrogenation after saturated after saturated.
20. methods as claimed in claim 19, while it is characterized in that the liquid of described liquid phase stream, volume space velocity is 0.1h
-1～20h
-1.
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| CN113375048B (en) * | 2021-04-23 | 2023-01-10 | 北京环宇京辉京城气体科技有限公司 | Hydrogen-returning device for hydrogen production by natural gas and hydrogen-returning process using same |
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