CN1277987A - Catalytic distillation selective hydrogenation process for cracking petroleum hydrocarbon vapor for producing C3 fraction composition - Google Patents
Catalytic distillation selective hydrogenation process for cracking petroleum hydrocarbon vapor for producing C3 fraction composition Download PDFInfo
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Abstract
The invented petroleum hydrocarbon steam cracking C3-fraction catalytic distillation selective hydrogenation process is to take material containing C3 and higher components and hydrogen to proceed hydrogenation in catalytic distillation tower, the selective hydrogenation catalyst used in catalytic distillation tower is directly spread on the catalyst bed lager, the free space exists inside the catalyst particle or/and between the particles, and the free space in the catalyst bed layer occupies 35-80% of the catalyst bed layer volume. The catalyst possesses dual functions of catalysis and fractionation, and it is high in reaction efficiency, no special internal is needed in reaction section, high in utilization rate of equipment, easy loading and unloading of catalyst, and long in service period.
Description
The present invention relates to the selection hydrogenation of propadiene in the cracking petroleum hydrocarbon vapor C3 fraction, propine height unsaturated hydrocarbons, particularly adopt catalytic distillation to select hydrogenation technique.
Traditional steam cracking product reclaims technology: split product is after waste heat boiler reclaims heat, gas-phase product enters compression, freezing, demethanizing, technological processs such as deethanizing, carbon three that obtains and above cut and compression condensate flow to into depropanizing tower, its overhead stream (C3 fraction) is again by selecting hydrogenation, fractionation by distillation obtains high-purity propylene, the tower still logistics of depropanizing tower enters debutanizing tower, its overhead stream enters the extractive distillation unit, isolate divinyl and remaining butylene, the butane logistics, the tower still logistics of debutanizing tower and cracking liquid product enter the pyrolysis gasoline hydrogenation of postorder, separating unit.See Fig. 9.
As above-mentioned, contain a certain amount of propine and propadiene (MAPD) in the C3 fraction that cracking petroleum hydrocarbon vapor obtains, industrial in order to obtain chemical grade or polymerization-grade propylene, need wherein alkynes and diolefin are removed by selecting hydrogenation, fractionation by distillation etc., as being removed to respectively less than 5ppm and 10ppm; Simultaneously, utilize the selectivity of hydrogenation process, make propine and propadiene be converted into propylene as much as possible, reducing the propylene deep hydrogenation is the amount of propane, to improve the yield of propylene.
Hydrocarbon vapours cracking product contains the carbon four about 30% through overdraft, separation from the logistics that the deethanizing column still obtains, butadiene content wherein reaches more than 40%, divinyl is important basic Organic Chemicals, is used for synthesizing butadiene styrene rubber, paracril, resin, nylon etc.
At present, adopting maximum selection hydrogen addition technologies both at home and abroad is fixed bed vapour phase or liquid-phase hydrogenatin technology, be generally two sections bed operations, by first section reactor, propine and propadiene transformation efficiency reach about 80%, for the control reaction temperature rising, generally will dilute raw material with part one-stage hydrogenation product in the production, increase the chance of propylene deep hydrogenation, be unfavorable for improving propene yield.In addition, because propadiene, easily polymerization on catalyzer of propine, the polymkeric substance that generates covers on the catalyst surface, because of can not in time removing activity of such catalysts is reduced, therefore will be along with the prolongation of runtime, improve constantly the mol ratio of hydrogen and propadiene, propine, propene yield is further reduced, and per 4～6 months need with catalyst regeneration once.
Catalytic distillation technology is to react and be separated in the same catalysis-distillation equipment to carry out.WO94/04477 discloses diolefine and alkynes catalytic distillation selection hydrogenation technique in a kind of carbon three logistics, and WO95/15934, CN1141622A have quoted from the full content of this patent.This technology is to be that the logistics and the hydrogen gas stream of main component causes in the catalytic distillation tower with the propylene with what contain propadiene, propine, small grain size catalyst pack in this tower is contained in the sack of making especially, leave the space that steam supply-the liquid phase material convection current is passed through between the sack, thereby make its packaging structure also play the effect of distillation filler, the small amount of carbon four above heavy constituent that contain in the charging are discharged from the tower still.This catalyst structure complexity with catalysis and fractional distillation functions, operation inconvenience, expense is higher, and because catalyst pack is contained in the pouch, and reactant must could contact or leave catalyzer through diffusion with resultant, this has also influenced reaction efficiency.
The catalytic distillation that the purpose of this invention is to provide the cracking petroleum hydrocarbon vapor C3 fraction is selected hydrogenation technique, selecting hydrogenation to be combined in the equipment with the catalytic distillation of carbon four and above fraction separation and C3 fraction in the carbon in the cracking petroleum hydrocarbon vapor three carries out, catalyzer in catalytic distillation tower does not need any packaging structure, catalysis and fractionation efficiency height, the effective rate of utilization height of equipment does not lose divinyl in selecting hydrogenation process.
The catalytic distillation of cracking petroleum hydrocarbon vapor C3 fraction of the present invention is selected hydrogenation technique, is to contain C
3And C
3The process that above material and hydrogen carry out in catalytic distillation tower, used selection hydrogenation catalyst is directly in bulk in catalytic distillation tower in the catalytic distillation tower, and the freeboard in the beds accounts for 35～80% of beds volume.
Described C
3And C
3Above material contains propadiene, propine, propylene, propane, divinyl, butylene, butane and a small amount of heavy constituent.Be the cracking petroleum hydrocarbon vapor product after waste heat boiler reclaims heat, gas-phase product enters the logistics of carbon three that technological processs such as compression, freezing, demethanizing, deethanizing obtain and above component and compresses the condensation logistics.
Catalyzer of the present invention has catalysis and fractionated dual-use function, and granules of catalyst inside can make the convection current of vapour-liquid phase materials pass through or/and freeboard is arranged between the particle.It directly fills in the conversion zone of catalytic distillation tower, and the liquid phase material that flows downward in the tower and the mobile vapor-phase material convection current that makes progress are reacted and fractionation by the reacting section catalyst bed.The freeboard that forms in the beds is preferably 40～60% of beds volume.Freeboard in the beds is made up of the inner formed freeboard of formed freeboard and granules of catalyst between the granules of catalyst, wherein formed freeboard accounts for 20～60% of beds volume between the granules of catalyst, be preferably 30～50%, the inner formed freeboard of granules of catalyst accounts for 15～60% of beds volume, is preferably 25～40%.
The equivalent diameter of catalyzer cross section is 5～100mm, is preferably 10～60mm, aspect ratio 0.5～1.5: 1.
The shape of above-mentioned catalyzer preferably has has concavo-convex outside surface, the inside that has has and is divided into many spatial muscle, have plenty of and have the two concurrently, have the vapour of making between granules of catalyst inside and the particle to increase the surface-area of catalyzer, to make, a freely through space of liquid phase material.Concavo-convex outside surface can be to be formed by structures such as dentation, groove shapes.
Catalyzer can be made into following different shape according to different needs:
(1) cross section is a honeycomb type, has big outside surface, and the carrying out that promptly helps reacting also helps improving its fractionation efficiency;
(2) cross section has bigger outside surface for the honeycomb type of band external tooth;
(3) cross section is a cartwheel pattern, has freeboard in the bigger particle, is applicable to bigger circulation;
(4) cross section is the cartwheel pattern of band external tooth, and circulation is bigger;
(5) cross section is for being with the ring-like of external tooth, and the freeboard maximum that it is inner is applicable to bigger vapour-liquid circulation;
(6) hollow trifolium-shaped;
(7) Raschig ring shape.
Or other similar shape.The shape of catalyzer and the selection of size are according to the flow decision of vapour, liquid phase material convection current in conversion zone in the tower.
Catalyzer is that dipping or spraying palladium or other have and select the metal of hydrogenation to form on the packing type skeleton structure that is made of aluminum oxide etc.Preferred skeleton structure is an alumina supporter, is to be to form in 4～10 hours in 900～1600 ℃ of following roastings after the material forming drying by powdery aluminium hydroxide, and optimum calcination temperature is 1100～1300 ℃.The specific surface of carrier is 10～100m after the roasting
2/ g is preferably 15～50m
2/ g, specific pore volume 0.2～0.7ml/g is preferably 0.3～0.6ml/g, and mean pore size 400～4000A is preferably 600～2000A.The activity of such catalysts component is based on VIII elements such as Pd, Ni, and the content of palladium or other metal is 0.01～5.0%, is preferably 0.2～0.5%.Palladium or metal preferably are distributed in carrier surface with eggshell type, and palladium layer thickness 0.1～0.5mm is preferably 0.1～0.2mm.Behind palladium-impregnated on the packing type skeleton structure or other metal, 80～160 ℃ down dry, then 200～600 ℃ of following roastings 1～10 hour, at last under 50～150 ℃ with hydrogen reducing or with solution reductions such as formic acid, formaldehyde.
Technology of the present invention is (see figure 9) C3 fraction in the traditional technology and carbon four above fraction separation towers (depropanizing tower) and two technological processs of C 3 fraction selective hydrogenation to be combined carry out in same catalytic distillation tower.To be the logistics of deethanizing Tata still with compression condensation logistics mix or enter catalytic distillation tower respectively, in catalytic distillation tower, under the effect of conventional separative element such as column plate or filler carbon four and above heavy constituent thereof are discharged from the tower still, forbid that particularly divinyl enters beds.Light constituents such as the carbon three in the charging, hydrogen are under centrifugation, top to tower moves into beds, under the effect of catalyzer, with unsaturated hydrocarbon selective hydrogenations such as wherein propadiene, propine is propylene, C3 fraction behind the selection hydrogenation refluxes through the condensation rear section from cat head, part enters propylene rectification tower, obtains highly purified polymerization-grade propylene or chemical grade propylene from cat head.
Catalytic distillation tower is formed (see figure 1) by four sections, the beds top of catalytic distillation tower is common distilling period I to cat head, and the reaction distillation section II that is made up of beds, beds bottom are to the common distilling period III of hydrocarbon stream opening for feed and the common distilling period VI below the hydrocarbon stream opening for feed.
Except propadiene, propine are selected to be hydrogenated to the propylene, also having is propane by saturated hydrogenation on a small quantity at the beds of reaction distillation section II, but the propylene total recovery is more than 100%.Particularly its underpart also has side reactions generations such as dimerization, poly in beds, but will leave beds under centrifugation in case generate polymkeric substance, enters common distilling period III, the IV of bottom, and discharges from the tower still.
Do not enter beds in order to ensure divinyl, common distilling period III has 5 above theoretical stages at least, is preferably 8～50, preferred 10～40; The number of theoretical plate of common distilling period IV is generally 10～40, is substantially devoid of carbon three components to guarantee the tower stilling in dividing, as being advisable less than 2%.Because in the logistics of beds top all is C3 fraction, do not need to be separated again, therefore can not establish common distilling period I, the boiling point of considering propadiene, propine is than propylene, propane height, common distilling period I helps to make propadiene in the carbon three, propylene at reaction distillation Duan Tinong, but come the billboard number unsuitable a lot of from economic angle,, be preferably 1～20 generally at 1～30.。
The tower top pressure of general control catalytic distillation tower is 1.5～2.5Mpa among the present invention, is preferably 1.5～2.2Mpa.The medial temperature of the reaction distillation section of catalytic distillation tower is 35～60 ℃.Per hour the ratio of the quality of C3 fraction and catalyst quality is between 10～30 in the charging, and the mol ratio of propadiene, propine sum is 1.2～4.0 in hydrogen feed amount and the hydrocarbon charging.
The present invention is a selection hydrogenation of finishing C3 fraction and carbon four and above fraction separation and C3 fraction in an equipment.The catalysis catalytic distillation tower is applied to the separation and selection hydrogenation process of C3 fraction, have following characteristics: 1, in catalytic distillation tower under vapour-liquid two phase separations, propadiene, propine are in catalyst active center after the selected hydrogenation, be easy to desorption and leave the active centre, reduced the chance of deep hydrogenation, help improving the selectivity of selecting hydrogenation, improve propene yield.2, diolefin and alkynes easily polymerization in fixed bed influences its activity on the polymkeric substance that forms on the catalyzer can be attached to catalyst surface; Use catalytic distillation technology then different, the dipolymer of formation or polymer can hightail beds and enter stripping section under centrifugation, the operational cycle of catalyzer is prolonged greatly.3, temperature of reaction is strict controlled in the boiling point of material under the reaction pressure, and reaction heat can only make the vaporization of more material, and bed can temperature runaway, helps improving propene yield.4, simplify technology, reduced energy consumption.The present invention makes propadiene, propine in the C3 fraction be converted into propylene to the technology of cracking petroleum hydrocarbon vapor C3 fraction catalytic distillation selection hydrogenation, and reducing the propylene deep hydrogenation is the amount of propane, does not lose divinyl simultaneously.The catalyzer that is adopted has big surface-area, have the difunctional of katalysis and fractionation, active high, the selectivity height, directly be seated in the beds of catalytic rectifying tower, freeboard is big, vapour, liquid phase material all directly convection current pass through beds, and directly contact with catalyzer, react simultaneously and the product fractionation, thereby the reaction efficiency height, conversion zone does not need special internals, simple in structure, the effective rate of utilization height of equipment, reduced investment, process cost is low, the filling of catalyzer and drawing off easily, the catalyzer life cycle is long, has prolonged work-ing life.
Further specify the present invention below in conjunction with process flow diagram and embodiment:
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is the cross sectional representation of cylindrical honeycomb catalyzer;
Fig. 3 is the cross sectional representation of the honeycombed catalyst of cylinder shape belt external tooth;
Fig. 4 is the cross sectional representation of cylindrical wheel shape catalyzer;
Fig. 5 is the cross sectional representation of the wheel shape catalyzer of cylinder shape belt external tooth;
Fig. 6 is the cross sectional representation of the ring-type catalyzer of cylinder shape belt external tooth;
Fig. 7 is the cross sectional representation of hollow trifolium-shaped catalyzer;
Fig. 8 is the cross sectional representation of Raschig ring shape catalyzer;
Fig. 9 is the process flow diagram of prior art.
As Fig. 1, split product is after waste heat boiler reclaims heat, gas-phase product enters the logistics of carbon three that technological processs such as compression, freezing, demethanizing, deethanizing obtain and above component and compression condensation logistics (being referred to as the hydrocarbon material import in the drawings) to be mixed or enters catalytic distillation tower respectively, in catalytic distillation tower, under the effect of conventional separative element such as column plate or filler carbon four and above heavy constituent thereof are discharged from the tower still, forbid that particularly divinyl enters beds.Light constituents such as the carbon three in the charging, hydrogen are under centrifugation, top to tower moves into beds, under the effect of catalyzer, with unsaturated hydrocarbon selective hydrogenations such as wherein propadiene, propine is propylene, C3 fraction behind the selection hydrogenation refluxes through the condensation rear section from cat head, part enters propylene rectification tower, obtains highly purified polymerization-grade propylene or chemical grade propylene from cat head.
Hydrogen can mix with hydrocarbon material and together enters in the tower, also can be in the arbitrary position among common distilling period III, the IV or its independent charging in watershed area place; Partly charging in the above described manner, part enters in the tower from arbitrary position, the middle part of reaction distillation section.
Catalyzer can directly be seated on the catalyzer back up pad of catalytic distillation tower reaction distillation section, when loaded catalyst is bigger, catalyzer can be divided into a plurality of beds, is generally 2～5.Beds can be established the catalyzer loading port, unload outlet in order to the loading and unloading catalyzer.Fig. 2～8 are several shapes of catalyzer.
In order to prevent divinyl polymerization in tower, can add suitable stopper with raw material, as Resorcinol, quinones, polyamine or the like, stopper also can or add in return tank in the beds bottom.
Embodiment:
Preparation of catalysts:
, add 3.5% concentration and be 10% nitric acid and 3～5% auxiliary agent (nitric acid, field mountain valley with clumps of trees and bamboo powder etc.) and mediate evenly to＜0.12mm with powdery aluminium hydroxide raw material pulverizing, make the wheel shape carrier of Φ 16 * 16 * 2.5mm with shaper.After under 120 ℃ dry 1.5～2.0 hours, be warming up to 350～800 ℃ of roastings and sloughed crystal water in 2 hours behind the airing, be warming up to 1200 ℃ of roastings then and obtained carrier 10kg in 6 hours.And the PdCl of preparation 0.006mol/l
244 liters of solution flood at normal temperatures to steeping fluid be colourless or slightly yellow make and contain the Pd amount on the catalyzer about 0.28%, and make the Pd layer thickness at 0.08～0.15mm, drying is 3 hours under 120 ℃, and again 400 ℃ of following roastings 4 hours, gained catalyst structure parameter is as follows:
Profile wheel shape
Diameter, mm 16
Highly, mm 16
Cylindrical and spoke thickness (muscle), mm 2.5
Side pressure strength, kg/cm 5.2
Pore volume, ml/g 0.38
Specific surface, m
2/ g 21
Average pore radius, dust 1750
Pd content, % (wt) 0.28
With 7.8 liters of reaction distillation sections that are seated in the catalytic distillation tower middle part of diameter 100mm of above-mentioned prepared catalyzer, 1 meter of loading height.Filling Φ 6 * 6mm Borad ring in the common distilling period, wherein beds top to the loading height of the common distilling period I of cat head is 1.5 meters, the beds bottom is 2.0 meters to the loading height of the common distilling period III of hydrocarbon opening for feed, and the loading height of the common distilling period IV that the hydrocarbon opening for feed is following is 1.0 meters.Raw material is formed (m/m): propane 2.36%, and propylene 63.87%, propadiene 1.37%, propine 1.02%, butylene 13.04%, butane 1.02%, divinyl 15.82%, other is 1.50% years old.Experimental result under the different operating condition is as follows:
| Tower top pressure, MPa | ???1.8 | ????1.8 | ??2.0 |
| The medial temperature of beds, ℃ | ????41 | ????41 | ???46 |
| Propadiene and propine in hydrogen/charging, mol/mol | ???1.5 | ???2.0 | ??1.5 |
| Weight/the catalyst weight of C3 fraction in the charging per hour, h -1 | ????15 | ????20 | ???20 |
| Overhead fraction is formed, % (m/m) | |||
| Propane | ???4.09 | ???4.23 | ??4.19 |
| Propylene | ???95.71 | ???95.57 | ??95.60 |
| Propadiene | ??0.0032 | Do not detect | Do not detect |
| Propine | Do not detect | Do not detect | Do not detect |
| Carbon four | Do not detect | Do not detect | Do not detect |
| The tower still is formed, % (m/m) | |||
| Propane | Do not detect | Do not detect | Do not detect |
| Propylene | Do not detect | Do not detect | Do not detect |
| Propadiene and propine | Do not detect | Do not detect | Do not detect |
| Divinyl | ??49.21 | ??49.39 | ??48.96 |
| Butylene | ??41.56 | ??41.63 | ??41.58 |
| Butane | ???3.25 | ??3.29 | ??3.33 |
| Other | ???5.98 | ??5.69 | ??6.13 |
Claims (17)
1, catalytic distillation selective hydrogenation process for cracking petroleum hydrocarbon vapor for producing C 3 fraction composition is characterized in that it being to contain C
3And C
3The process that the material of above component and hydrogen carry out in catalytic distillation tower, used selection hydrogenation catalyst is directly in bulk in catalytic distillation tower in the catalytic distillation tower, and the freeboard in the beds accounts for 35～80% of beds volume.
2, technology according to claim 1 is characterised in that the freeboard in the beds accounts for 40～60% of beds volume.
3, technology according to claim 1, be characterised in that formed freeboard accounts for 20～60% of beds volume between the granules of catalyst, be preferably 30～50%, the inner formed freeboard of granules of catalyst accounts for 15～60% of beds volume, is preferably 25～40%.
4, technology according to claim 1 is characterised in that the equivalent diameter of catalyzer cross section is 5～100mm, is preferably 10～60mm, aspect ratio 0.5～1.5: 1.
5, according to claim 1,3,4 described technologies, be characterised in that catalyzer have concavo-convex outside surface or (with) inside has and is divided into many spatial muscle.
6,, it is characterized in that catalyzer is any in the following shape according to claim 1,3,4 described technologies:
(1) cross section is a honeycomb type;
(2) cross section is the honeycomb type of band external tooth;
(3) cross section is a cartwheel pattern;
(4) cross section is the cartwheel pattern of band external tooth;
(5) cross section is for being with the ring-like of external tooth;
(6) hollow trifolium-shaped;
(7) Raschig ring shape.
7, technology according to claim 1 is characterised in that catalyzer is that dipping or spraying palladium or other have and select the metal of hydrogenation to form on the packing type skeleton structure that is made of aluminum oxide etc.
8, technology according to claim 7 is characterized in that alumina supporter is is to form in 4～10 hours in 900～1600 ℃ of following roastings after the material forming drying by powdery aluminium hydroxide, and optimum calcination temperature is 1100～1300 ℃.
9, according to claim 7,8 described technologies, the specific surface that is characterised in that support of the catalyst is 10～100m
2/ g is preferably 15～50m
2/ g, specific pore volume 0.2～0.7ml/g is preferably 0.3～0.6ml/g, and mean pore size 400～4000 are preferably 600～2000 .
10, according to claim 7,8 described technologies, be characterised in that the content of palladium or other metal is 0.01～5.0%, be preferably 0.2～0.5%.
11, technology according to claim 10 is characterised in that palladium or metal are distributed in carrier surface with eggshell type, and palladium or metal layer thickness 0.1～0.5mm are preferably 0.1～0.2mm.
12, technology according to claim 7, be characterised in that behind palladium-impregnated on the packing type skeleton structure or other metal, 80～160 ℃ down dry, then 200～600 ℃ of following roastings 1～10 hour, at last under 50～150 ℃ with hydrogen reducing or with solution reductions such as formic acid, formaldehyde.
13, technology according to claim 1, be characterised in that catalytic distillation tower comprises that the reaction distillation section II that is made up of beds, beds bottom are to the common distilling period III of hydrocarbon stream opening for feed and the common distilling period IV below the hydrocarbon stream opening for feed, wherein common distilling period III has 5 above theoretical stages at least, be preferably 8～50, the number of theoretical plate of common distilling period IV is 10～40.
14, technology according to claim 13 is characterised in that the beds top of catalytic distillation tower is common distilling period I to cat head, and its number of theoretical plate is 1～30, is preferably 1～20.
15, technology according to claim 1 is characterised in that the tower top pressure of catalytic distillation tower is 1.5～2.5Mpa, is preferably 1.5～2.2Mpa.
16, according to claim 1,13 described technologies, the medial temperature that is characterised in that the reaction distillation section of catalytic distillation tower is 35～60 ℃.
17, technology according to claim 1, the mol ratio that is characterised in that propadiene in hydrogen and the charging, propine sum is 1.2～4.0, per hour the ratio of the quality of C3 fraction and catalyst quality is 10～30 in the charging.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906015A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C3 fractions |
| CN102477111A (en) * | 2010-11-30 | 2012-05-30 | 中国石油化工股份有限公司 | Method for hydrogenating polymer |
| CN101906014B (en) * | 2009-09-15 | 2013-07-31 | 中国石油天然气股份有限公司 | C2 fraction selective hydrogenation method |
| CN103772111A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalytic hydrogenation method of rubber plant tail gas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946815A (en) * | 1988-12-23 | 1990-08-07 | Uop | Solid phosphoric acid catalyst |
| CN1045305C (en) * | 1995-12-20 | 1999-09-29 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
-
1999
- 1999-06-16 CN CN99112272A patent/CN1087334C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906015A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C3 fractions |
| CN101906014B (en) * | 2009-09-15 | 2013-07-31 | 中国石油天然气股份有限公司 | C2 fraction selective hydrogenation method |
| CN101906015B (en) * | 2009-09-15 | 2013-09-04 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C3 fractions |
| CN102477111A (en) * | 2010-11-30 | 2012-05-30 | 中国石油化工股份有限公司 | Method for hydrogenating polymer |
| CN102477111B (en) * | 2010-11-30 | 2013-08-14 | 中国石油化工股份有限公司 | Method for hydrogenating polymer |
| CN103772111A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalytic hydrogenation method of rubber plant tail gas |
| CN103772111B (en) * | 2012-10-24 | 2016-01-06 | 中国石油化工股份有限公司 | The tail gas catalyzed method of hydrotreating of a kind of rubber plant |
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| Publication number | Publication date |
|---|---|
| CN1087334C (en) | 2002-07-10 |
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