CN101279279B - Method for selective hydrogenation - Google Patents
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Abstract
The present invention relates to a method for selective hydrogenation which mainly solves the technical problems of low temperature, low activity and poor stability of the catalyst in the prior technology. The present invention better solves the problems by adopting the technical proposal that the catalyst includes the following components: (a) 5.0 to 40.0 percent of metal nickel or other oxides; (b) 0.01 to 20.0 percent of at least one element or the oxide thereof selected from Mo or W; (c) 0.01 to 10.0 percent of at least one element or the oxide thereof selected from the rare earth; (d) 0.01 to 2.0 percent of at least one element or the oxide thereof selected from the IA or IIA in the element periodic table; (e) 0 to 15.0 percent of at least one element or the oxide thereof selected from Si, P, B or F; (f) 0 to 10 percent of at least one element or the oxide thereof selected from the IVB in the element periodic table; (g) the rest amount is a carrier of alumina; wherein, the specific surface of the carrier is 100 to 180 m<2>/g; the total pore volume is 0.5 to 1.2ml/g. The present invention can be used for the industrial production of pyrolysis gasoline selective hydrogenation.
Description
Technical field
The present invention relates to a kind of method that is used for selective hydrogenation, particularly is the Raney nickel of the pyrolysis gasoline hydrogenation of 204 ℃ hydrocarbon compound full-cut fraction pyrolysis gasoline or C6～C8 hydrocarbon compound midbarrel about a kind of C5 of being used for hydrocarbon～do.
Background technology
The utilization of drippolene is to improve one of main path of device overall economic efficiency in the ethylene unit.Because drippolene is formed complicated, poor heat stability, usually, remove alkadienes and styrene through one-stage selective hydrogenation earlier, after the secondary hydrogenation desulfurization, be mainly used in the aromatic hydrocarbons extracting.It mainly is Pd system or Ni series catalysts with catalyst that present industrial drippolene is selected hydrogenation, midbarrel (C
6～C
8The hydrocarbon compound cut) hydrogenation or full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) hydrogenation technique.Because the difference of each ethylene unit cracking stock and cracking condition, each installs drippolene raw material composition and differs bigger, and particularly the diene of drippolene, colloid and As, content of beary metal exist than big-difference; The device raw pyrolysis gasoline diene, the colloid height that have, and toxic content such as colloid and As, heavy metal is higher in the device raw pyrolysis gasoline raw material that has, toxic contents such as individual device raw pyrolysis gasoline diene, colloid and As, heavy metal are all high, these all can cause operating operating mode and worsen the easy inactivation of Pd series catalysts.Therefore, although traditional Pd series catalysts has been obtained effect preferably in commercial Application, but still have certain limitation, especially to containing the higher raw material of As, the Pd series catalysts often is difficult to satisfy the needs of operation steady in a long-term under harsh working condition.Anti-As performance that Ni is catalyst based and low-temperature stability make it have important purposes in drippolene especially full-cut fraction pyrolysis gasoline process for selective hydrogenation, raw material need not to take off As and handles, thereby save a large amount of operating costs, and reduce catalyst causes active decline because of the As accumulation parking regeneration expense; Ni is catalyst based, and to compare price lower with the Pd series catalysts; Low form Ni is catalyst based at cracking by-product such as C
4, C
5, C
9Hydrogenation utilize the aspect will bring into play and important effect.Therefore, Ni is catalyst based is applied to full cut or selects the cut fraction pyrolysis gasoline selective hydrogenation to have good prospect at replacement Pd series catalysts.
Full-cut fraction pyrolysis gasoline is rich in C
5, C
9 +(carbon nine and more than) unsaturated component, the diene height, easily polymerization, colloid (high molecular polymer that unsaturated component polymerization reaction take place such as alkadienes and styrene generates) height, heavy ends are many, coke powder content height, poor stability, lack effective water-oil separating means owing to form azeotropic mixture or commercial plant, cause raw material free water content height, poisonous substances such as heavy metal easily are enriched in C
9 +In (carbon nine and more than) cut and characteristics such as the hydrogenation thermal discharge is big, make the very fast inactivation of catalyst, thereby catalyst have to frequent activation and regeneration.The Ni/Al of present commercial Application
2O
3Catalyst is difficult to adapt in the ethylene industry requirement of the frequent fluctuation of raw material quality in the drippolene one-stage hydrogenation and high selectivity, high-speed and long-term operation, be still waiting to improve in diene low temperature hydrogenation activity, selectivity, air speed and aspects such as interference free performance such as water-fast, wish that hydrogenation catalyst has better anti-interference, suitable appearance glue ability, higher low temperature active and selectivity, increasing the catalyst regeneration cycle, thereby prolong catalyst service life.
A kind of hydrogenation catalyst and technology and application are disclosed among the Chinese patent CN1644656A.This catalyst weight percentage consists of NiO 10～30%, Al
2O
370～90%.This catalyst is applicable to the distillate that contains alkadienes and styrene and derivative thereof, and reaction process condition is 50～200 ℃ of temperature, pressure 2.0～4.0MPa, liquid air speed 1～10 hour
-1, hydrogen to oil volume ratio is H
2This catalyst and technology directly high aromatic solvent naphtha of hydrogenation preparing and high-knock rating gasoline are adopted in/oil=100～300.The shortcoming of this catalyst is the preparation process complexity of catalyst carrier, and carrier needs to feed steam reaming 1～4 hour at 600～700 ℃, and roasting then just can obtain the carrier of high-ratio surface, macropore.
A kind of selective hydrocatalyst is disclosed among the Chinese patent CN1218822A.This catalyst is by the NiO of 5～25 heavy %, and 0.1～2.0 weighs lithium or the alkaline-earth metal (preferably magnesium) of %, and the aluminium oxide of surplus composition, is applicable to the selective hydrogenation process of the full distillate oil of the distillate that contains diolefin, particularly drippolene.The shortcoming of this catalyst is that the specific area of catalyst is lower (60～85 meters
2/ gram), pore volume less (0.28～0.36 milliliter/gram), reactivity is relatively low, reaction temperature higher (80～160 ℃).
Technical problem to be solved by this invention be exist the low temperature active of catalyst low in the prior art, the technical problem of poor stability, a kind of new method that is used for selective hydrogenation is provided.Catalyst system therefor is applicable to C
6～C
8Hydrocarbon compound midbarrel and full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) pyrolysis gasoline hydrogenation, and have the advantage of good low temperature active, selectivity and stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for selective hydrogenation, be used for C6～C8 hydrocarbon compound midbarrel and full-cut fraction pyrolysis gasoline hydrogenation, the big pore volume nickel catalyst comprises following component by weight percentage: (a) 5.0～40.0% metallic nickel or its oxide; (b) 0.01～20.0% be selected from least a element or its oxide in molybdenum or the tungsten; (c) 0.01～10.0% be selected from least a element or its oxide in the rare earth; (d) 0.01～2.0% be selected from least a element or its oxide among I A in the periodic table of elements or the II A; (e) 0～15.0% be selected from least a element or its oxide in silicon, phosphorus, boron or the fluorine; (f) 0～10.0% be selected from least a element among the IV B or its oxide in the periodic table of elements; (g) alumina catalyst support of surplus; Wherein the specific area of carrier is 100～180 meters
2/ gram, total pore volume are 0.5～1.2 milliliter/gram.
In the technique scheme, by weight percentage, the content preferable range of metallic nickel or its oxide is 10.0～30.0% in the catalyst; Being selected from least a element in molybdenum or the tungsten or the content preferable range of its oxide is 0.1～15.0%; Being selected from least a element in the rare earth or the content preferable range of its oxide is 0.1～5.0%; Being selected from least a element among I A in the periodic table of elements or the II A or the content preferable range of its oxide is 0.2～0.8%; Being selected from least a element in silicon, phosphorus, boron or the fluorine or the content preferable range of its oxide is 0.5～10.0%; The content preferable range that is selected from least a element among the IV B in the periodic table of elements or its oxide is 0.1～5.0%.The element preferred version that is selected from the rare earth is at least a for being selected from lanthanum or the cerium; The element preferred version that is selected from I A in the periodic table of elements is a potassium; The element preferred version that is selected from II A in the periodic table of elements is at least a for being selected from calcium, magnesium or the barium; The element preferred version that is selected from IV B in the periodic table of elements is at least a for being selected from titanium or the zirconium.Carrier specific area preferable range is 120～160 meters
2/ gram, total pore volume preferable range are 0.8～1.1 milliliter/gram.
The preparation method of carrier of the present invention comprise with aluminium oxide and modifier, peptizing agent, water mix in the desired amount, behind the extruded moulding, earlier 50～120 ℃ dry 1～24 hour down, then 700～1150 ℃ of following roastings 1～10 hour, obtain carrier.
Preparation of catalysts method of the present invention is: with the solution impregnation that carrier is made into the cocatalyst component of using in the nickel compound of aequum and the catalyst, the soaked carrier drying, 350～500 ℃ of roastings promptly get the oxidative catalyst finished product in air.Can repeat above-mentioned steps and make required nickel content.Finished catalyst need be used hydrogen reducing before use.
Catalyst of the present invention is applicable to the alkynes of petroleum hydrocarbon or the selection hydrogenation of diolefin, is preferably the full cut (C of drippolene
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) or C
6～C
8The hydrogenation of hydrocarbon compound midbarrel.
Catalyst of the present invention is being used for full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) have good low temperature active, selectivity and stability during the drippolene selective hydrogenation.At 50 ℃ of inlet temperatures, reaction pressure 2.7MPa, hydrogen/oil volume ratio is 100: 1, green oil air speed 3.8 hours
-1, total air speed 7.6 hours
-1Under the condition, to full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene carries out selective hydrogenation reaction, and its outlet diene mean value is 0.4 gram iodine/100 gram oil, and the diolefin hydrogenation rate is 98.0%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.But these embodiment in no case are construed as limiting scope of the present invention.
The specific embodiment
[embodiment 1]
Take by weighing boehmite 300 grams, 150 gram alpha-aluminium oxides, 9 gram sesbania powder mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 4.0 grams, concentration are 85% phosphatase 11 .8 gram, potassium nitrate 1.5 grams, 360 milliliters of the aqueous solution of magnesium nitrate 2 grams, be extruded into the clover of 2.5 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 1150 ℃ of roastings 2 hours, obtain carrier Z1.Take by weighing ammonium molybdate 2.5 gram, lanthanum nitrate 1.0 grams, zirconium nitrate 4.0 grams add entry 130 grams, are that 14% nickel liquid 50 grams mix and are made into maceration extract with concentration.Carrier is carried out equivalent impregnation in maceration extract, 60 ℃ of dryings 8 hours, 450 ℃ of roastings 4 hours make the catalyst based C1 of Ni, and making final Ni content is 10.0% of alumina catalyst support weight.Catalyst composition, specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 2]
Adopt carrier Z2, the preparing carriers method is with embodiment 1, and vehicle group becomes to see Table 1.Take by weighing ammonium molybdate 10.0 gram, ammonium tungstate 5.0 grams, lanthanum nitrate 3.5 grams, cerous nitrate 3.0 grams, titanium chloride 4.5 grams, potassium borohydride 2.0 grams, potassium fluoride 3.0 grams add entry 30 grams, are that 14% nickel liquid 150 grams mix and are made into maceration extract with concentration.Make the catalyst based C2 of Ni with embodiment 1 same operating procedure and condition, making final Ni content is 30.0% of alumina catalyst support weight.Catalyst composition, specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 3]
Take by weighing boehmite 300 grams, 45 gram diatomite, 9 gram sesbania powder, mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 3.5 grams, 360 milliliters of the aqueous solution of calcium nitrate 1.0 grams, be extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 750 ℃ of roastings 4 hours, obtain carrier Z3.Take by weighing ammonium molybdate 25 gram, cerous nitrate 3.0 grams, zirconium nitrate 0.5 gram adds entry 80 grams, is that 14% nickel liquid 100 grams mix and are made into maceration extract with concentration.Make the catalyst based C3 of Ni with embodiment 1 same operating procedure and condition, making final Ni content is 20.0% of alumina catalyst support weight.Catalyst composition, specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 4]
Take by weighing boehmite 345 grams, 9 gram sesbania powder, mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 3.5 gram, 345 milliliters of the aqueous solution of calcium nitrate 1.0 grams are extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 750 ℃ of roastings 4 hours, obtain carrier Z4.Take by weighing ammonium tungstate 8 gram, lanthanum nitrate 3 grams, zirconium nitrate 0.5 gram adds entry 70 grams, is that 14% nickel liquid 100 grams mix and are made into maceration extract with concentration.Make the catalyst based C4 of Ni with embodiment 1 same operating procedure and condition, making final Ni content is 20.0% of alumina catalyst support weight.Catalyst composition, specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[embodiment 5]
Take by weighing boehmite 300 grams, 45 gram diatomite, 9 gram sesbania powder, mix, add afterwards and contain poly-vinyl alcohol solution (mass concentration is 5%) 25 grams, nitric acid 3.5 grams, 360 milliliters of the aqueous solution of calcium nitrate 1.0 grams, be extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 750 ℃ of roastings 4 hours, obtain carrier Z5.Take by weighing ammonium molybdate 17 gram, cerous nitrate 3.0 grams add entry 85 grams, are that 14% nickel liquid 100 grams mix and are made into maceration extract with concentration.Make the catalyst based C5 of Ni with embodiment 1 same operating procedure and condition, making final Ni content is 20.0% of alumina catalyst support weight.Catalyst composition, specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
[comparative example 1]
Take by weighing boehmite 300 gram, 9 gram sesbania powder, 45 gram graphite mix, and are extruded into the clover of 2.5 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 1050 ℃ of roastings 4 hours, obtain carrier D1.Make the catalyst based CD1 of Ni with embodiment 1 same operating procedure and condition, making final Ni content is 20% of alumina catalyst support weight.Catalyst composition, specific area, pore volume see Table 1, and wherein each constituent content is all in alumina catalyst support weight.
Table 1
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 | Comparative example 1 |
| The catalyst numbering | C1 | C2 | C3 | C4 | C5 | CD1 |
| Bearer number | Z1 | Z2 | Z3 | Z4 | Z5 | D1 |
| Ni content, % (weight) | 10 | 30 | 20 | 20 | 20 | 20 |
| Molybdenum, W elements content, % (weight) | Mo-0.1 | Mo-5.0 W-5.0? | Mo-15.0 | W-10.0 | Mo-10.0 | ?0 |
| Ree content, % (weight) | La-0.1 | La-2.5 Ce-2.5 | Ce-2.5 | La-2.5 | Ce-2.5 | ?0 |
| The IA constituent content, % (weight) | K-0.3 | K-0.5 | 0 | 0 | 0 | 0 |
| The IIA constituent content, % (weight) | Mg-0.5 | Ba-0.1 | Ca-0.2 | Ca-0.2 | Ca-0.2 | 0 |
| Silicon, phosphorus, boron, fluorine element content, % (weight) | P-0.5 | B-5.0 F-5.0 | Si-10.0 | ?0 | Si-10.0 | ?0 |
| The IVB constituent content, % (weight) | Zr-2.5 | Ti-5.0 | Zr-0.1 | Zr-0.1 | 0 | 0 |
| Specific area, rice 2/ gram | 122.4 | 138.7 | 157.2 | 129.3 | 148.6 | 102.3 |
| Pore volume, milliliter/gram | 1.05 | 0.91 | 0.84 | 0.99 | 0.88 | 0.56 |
[embodiment 6]
Present embodiment explanation embodiment 1～5 gained catalyst is at full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene selects the application in the hydrogenation.
Getting each 80 milliliters of the embodiment of the invention 1～5 catalyst, is 2.7MPa at Hydrogen Vapor Pressure, and temperature is that 450 ℃ and hydrogen flowing quantity are reduction 12 hours under the condition of 1500 ml/min.At Hydrogen Vapor Pressure 2.7MPa, 50 ℃ of inlet temperatures, green oil air speed 3.8 hours
-1(total air speed 7.6 hours
-1), feed the full-cut fraction pyrolysis gasoline raw material under the condition of hydrogen/oil volume than 100: 1 and test.Full-cut fraction pyrolysis gasoline raw material weight percentage consists of C
5Hydrocarbon 15.5%, C
6Hydrocarbon 21.8%, C7 hydrocarbon 23.3%, C
8Hydrocarbon 21.3%, C
9 +Hydrocarbon 18.1%, diene value 27.12.Hydrogenation the results are shown in Table 2.
[comparative example 2]
Get comparative example 1 catalyst CD180 milliliter, reduce with embodiment 6 same conditions.Test with embodiment 6 same raw material, reaction conditions, hydrogenation the results are shown in Table 2.
Table 2
[embodiment 7]
2 catalyst C2 are at full cut (C for the present embodiment explanation embodiment of the invention
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene selects in the hydrogenation 1000 hours result of the test.
Get embodiment 2 catalyst C280 milliliters, repeat the reduction process of embodiment 6,50 ℃ of temperature, reaction pressure 2.65MPa, green oil air speed 3.8 hours
-1(total air speed 7.6 hours
-1), feed the full-cut fraction pyrolysis gasoline raw material under the condition of hydrogen/oil volume than 100: 1 and test.Full-cut fraction pyrolysis gasoline raw material weight percentage consists of C
5Hydrocarbon 15.5%, C
6Hydrocarbon 21.8%, C
7Hydrocarbon 23.3%, C
8Hydrocarbon 21.3%, C
9 +Hydrocarbon 18.1%, diene value 27.12.Hydrogenation the results are shown in Table 3.
[comparative example 3]
Get comparative example 1 catalyst CD180 milliliter, reduce with embodiment 6 same conditions.Test with embodiment 7 same raw material, reaction conditions, hydrogenation the results are shown in Table 3.
Table 3
[embodiment 8]
2 catalyst C2 are at C for the present embodiment explanation embodiment of the invention
6～C
81000 hours result of the test in the drippolene selection hydrogenation of hydrocarbon compound midbarrel.
Get embodiment 2 catalyst C280 milliliters, repeat the reduction process of embodiment 6,50 ℃ of temperature, reaction pressure 2.65MPa, green oil air speed 3.0 hours
-1(total air speed 7.5 hours
-1), feed C6～C8 midbarrel drippolene raw material under the condition of hydrogen/oil volume than 110: 1 and test.C6～C8 midbarrel drippolene raw material weight percentage consists of C
6Hydrocarbon 32.8%, C7 hydrocarbon 35.1%, C
8Hydrocarbon 32.1%, diene value 23.99 gram iodine/100 gram oil.Hydrogenation the results are shown in Table 4.
Table 4
| Reaction time (hour) | The average diene of product (gram iodine/100 gram oil) | Average diolefin hydrogenation rate (%) |
| 50 | 0.52 | 97.40 |
| 100 | 0.73 | 96.35 |
| 150 | 0.66 | 96.70 |
| 200 | 0.84 | 95.80 |
| 250 | 0.62 | 96.90 |
| 300 | 0.77 | 96.15 |
| 350 | 0.57 | 97.15 |
| 400 | 0.65 | 96.75 |
| 450 | 0.42 | 97.90 |
| 500 | 0.58 | 97.10 |
Claims (4)
1. a method that is used for selective hydrogenation is used for C6～C8 hydrocarbon compound midbarrel and full-cut fraction pyrolysis gasoline hydrogenation, and the big pore volume nickel catalyst is composed of the following components by weight percentage:
(a) 5.0～40.0% metallic nickel or its oxide;
(b) 0.01～20.0% be selected from least a element or its oxide in molybdenum or the tungsten;
(c) 0.01～10.0% be selected from least a element or its oxide in the rare earth;
(d) 0.01～2.0% be selected from least a element or its oxide among IA in the periodic table of elements or the IIA;
(e) 0～15.0% be selected from least a element or its oxide in silicon, phosphorus, boron or the fluorine;
(f) 0～10.0% be selected from least a element among the IVB or its oxide in the periodic table of elements;
(g) alumina catalyst support of surplus;
Wherein the specific area of carrier is 100～180 meters
2/ gram, total pore volume are 0.5～1.2 milliliter/gram.
2. according to the described method that is used for selective hydrogenation of claim 1, it is characterized in that by weight percentage that the content of metallic nickel or its oxide is 10.0～30.0% in the catalyst; Being selected from least a element in molybdenum or the tungsten or the content of its oxide is 0.1～15.0%; Being selected from least a element in the rare earth or the content of its oxide is 0.1～5.0%; Being selected from least a element among IA in the periodic table of elements or the IIA or the content of its oxide is 0.2～0.8%; Being selected from least a element in silicon, phosphorus, boron or the fluorine or the content of its oxide is 0.5～10.0%; The content that is selected from least a element among the IVB in the periodic table of elements or its oxide is 0.1～5.0%.
3. according to the described method that is used for selective hydrogenation of claim 1, the element that it is characterized in that being selected from the rare earth is selected from lanthanum or the cerium at least a; The element that is selected from IA in the periodic table of elements is a potassium; Be selected from that the element of IIA is selected from calcium, magnesium or the barium at least a in the periodic table of elements; Be selected from that the element of IVB is selected from titanium or the zirconium at least a in the periodic table of elements.
4. according to the described method that is used for selective hydrogenation of claim 1, the specific area that it is characterized in that carrier is 120～160 meters
2/ gram, total pore volume are 0.8～1.1 milliliter/gram.
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| CN102618328B (en) * | 2011-01-31 | 2015-02-11 | 北京安耐吉能源工程技术有限公司 | Gasoline processing method |
| CN102649066A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for phenylacetylene under the presence of styrene |
| CN102649065A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of phenylacetylene in presence of styrene |
| CN103030487B (en) * | 2011-09-29 | 2016-02-10 | 中国石油化工股份有限公司 | The method that aromatic hydrogenation is saturated |
| CN103418395B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN103418414B (en) * | 2012-05-16 | 2016-12-14 | 中国石油化工股份有限公司 | Catalyst for 4 nitrodiphenyl amine hydrogenation |
| CN102939994B (en) * | 2012-11-26 | 2014-05-07 | 河海大学 | Method for preparing silver/copper modified K4Nb6O17 film |
| US10518251B2 (en) * | 2015-05-29 | 2019-12-31 | Advanced Refining Technologies Llc | High HDN selectivity hydrotreating catalyst |
| CN107159283B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of method of cracking c5-C9 fraction selective hydrogenation |
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| CN101147871A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel catalyst for selective hydrogenation |
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