CN1188494C - Selective hydrogenation catalyst and its preparation method and application - Google Patents
Selective hydrogenation catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a selective hydrogenation catalyst and a preparation method and an application thereof for C-5-fraction. The catalyst uses aluminum oxides as a carrier, and contains at least one kind of metal of a group IB in a periodic table, at least one kind of the metal of a group VIII in the periodic table, and at least one kind of alkali metal. The catalyst is prepared through the steps: firstly, dipping the metal of the group IB; then, dipping the metal of the group VIII; finally, dipping the alkali metal. After each dipping step, the metal is dried within a temperature range of 50 to 200 DEG C, and is calcined within the temperature range of 250 to 650 DEG C. Acetylene hydrocarbon in the C-5-fraction is selected for hydrogenization through the catalyst, and the method is carried out in gas phases or gas-liquid phases. The temperature range is 30 to 70 DEG C, a pressure range is 0.1 to 4.0MPa, liquid space velocity is (2-12m#+3) to (m#+3). h, and the flow rate of hydrogen uses that the acetylene hydrocarbon is removed and the loss of the C-5-fraction is little as a reference.
Description
Technical field
The present invention relates to a kind of selective hydrogenation and remove the alkynes Catalysts and its preparation method, and relate to a kind of method of using these catalyzer the unsaturated compound in the hydrocarbon material to be carried out selective hydrogenation.Specifically, the present invention relates to a kind of is the multimetallic catalyst and preparation method thereof of carrier with the aluminum oxide, and relate to the method that the alkynes in alkynes, the especially isoprene in a kind of C5 fraction that C5 fraction is not particularly contained cyclopentadiene (dicyclopentadiene) carries out selective hydrogenation.
Background technology
The C5 fraction that petroleum cracking system ethylene by-product is a large amount of, its major ingredient is isoprene, m-pentadiene, cyclopentadiene, dicyclopentadiene, monoolefine and alkane, its separation and utilization are to improving the economic benefit of ethylene unit, and utilize resources synthetically has realistic meaning.The diolefin that accounts for C5 fraction 40-60% usually will be through separating the technology of purifying, and could rationally utilize effectively after reaching certain purity.Because C5 fraction is formed complicated, boiling point is approaching and easily generate azeotrope each other, and therefrom isolating the higher carbon of added value five dienes is very complex engineering.Isolated isoprene is mainly used in polymerization and generates polyisoprene rubber, specialty elastomer, SIS isoprene-isobutylene rubber, is important Organic Chemicals.The alkynes of trace produces injurious effects to the isoprene polymerization catalyzer in the isoprene.
In order to produce highly purified carbon five dienes, the separation method of industrial widespread usage is that the solvent extraction distillation method is promptly removed alkynes with extraction agent at present.But defectives such as this method has operation energy consumption and investment cost is higher, the loss of solvent and isoprene is bigger, and in the cycling extraction solvent, easily produce black bits occluding device.
Alkynes in the C5 fraction is carried out selective hydrogenation, thereby the method that obtains highly purified carbon five dienes has a spot of open.Promptly all or part of alkynes in the C5 fraction is carried out selective hydrogenation, especially generate desirable product in the C5 fraction by selective hydrogenation, in order to reduce the loss of corresponding valuable component, if possible, should avoid " excessive " hydrogenation to generate as far as possible and generate corresponding more high-grade compound than more saturated compound of desirable product and the parallel hydrogenation of product that contains unsaturated link(age).For example, hydrogenation such as valylene, 2-butyne, 1-pentyne in the C5 fraction are generated isoprene, 2-butylene, 1-amylene etc., perhaps make its residual content reach several ppm (by weight) at least, avoid " excessive " hydrogenation to make it change into more monoolefine and alkane as far as possible.This alkynes method of removing can be simplified carbon five separation process, but employed catalyzer needs higher selectivity, sufficiently high activity and sufficiently long work-ing life, long-term to be suitable for, low-cost running.
US3,912,789 (1975) disclose a kind of liquid phase hydrogenating catalyst.This catalyzer is main active constituent with copper, with other a kind of multivalence reactive metal for helping active constituent, for example silver, platinum, palladium, nickel, manganese, cobalt, chromium and molybdenum, adopting the gamma-alumina of the high-ratio surface that contains a certain amount of sodium oxide is carrier, specific surface is at least 10m
2/ g.This catalyst life is shorter, is 175-200 hour only, needs repeatedly regeneration.The temperature of hydrogenation reaction is 50 ℃-100 ℃, and service temperature is higher, makes the C 5 diene material be easy to polymerization.Catalyst selectivity is relatively poor, and the diolefin loss is bigger, and it is less to handle load.
US4,064,190 (1977) disclose a kind of gas-phase catalytic hydrogenation catalyst.This catalyzer is main active constituent with the copper that is carried on Zinc aluminate, with tin or plumbous for helping component.Service temperature is 121 ℃-427 ℃, and too high service temperature makes it have fatal shortcoming, and the reaction times is shorter, only is 0.02-5 minute.
Normally used this hydrogenation of unsaturated hydrocarbons catalyzer also has noble metal catalyst, and wherein noble metal loading is on support of the catalyst.Palladium is the precious metal that often uses, and carrier is porous inorganic oxide normally, the mixture of silicon-dioxide, silico-aluminate, titanium dioxide, zirconium dioxide and/or these carriers for example, but what often use is aluminum oxide or silicon-dioxide.Promotor or other additive can also be arranged usually.
But, the Catalyst And Method that the alkynes that is present in the C5 fraction is carried out selective hydrogenation, prior art can't satisfy the residual content that reduces alkynes behind the hydrogenation simultaneously and increase its selectivity, makes the loss amount of diolefine in the C5 fraction be reduced to a certain degree requirement.
Summary of the invention
The objective of the invention is defective at hydrogenation of unsaturated hydrocarbons catalyst life in the prior art is short, load is little, selectivity is relatively poor, provide a kind of selectivity height, good stability, long Catalysts and its preparation method and using method of life-span, can be effectively in the C5 fraction, the alkynes that does not particularly contain in C5 fraction, the especially isoprene of cyclopentadiene (dicyclopentadiene) carries out selective hydrogenation.
The invention provides a kind of is the multimetallic catalyst of carrier with the aluminum oxide, it is characterized in that this catalyzer comprises following component: (gross weight with catalyzer is a benchmark)
(1) I B-group metal at least a periodic table of elements, content is 0.1%-10%, preferred 1.0%-8%, more preferably 2%-6%; Copper accounts for more than 90% of gross weight content of this family metal in this family's metal, is preferably more than 95%, is preferably 99% especially, and other this family metal is a surplus;
(2) the group VIII metal at least a periodic table of elements, content is 0.008%-1%, preferred 0.01%-0.2%, more preferably 0.01%-0.1%;
(3) at least a basic metal, content are 0.01%-5%, preferred 0.1-2%, more preferably 0.2-1%.
IB family in the periodic table of elements is made up of elemental copper, silver and gold, and group VIII is made up of elemental iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum.As I B-group metal, preferably copper, silver-colored bimetal as this family; As the group VIII metal, this catalyzer can comprise nickel, palladium, platinum and/or rhodium, and preferred palladium is the single metal of this family; Basic metal comprises lithium, sodium, potassium etc., and preferred potassium is as the single metal of this family.This activity of such catalysts component preferably includes copper, silver, palladium and potassium.
If necessary or need, this activity of such catalysts component can also comprise other element beyond periodic table of elements group VIII, IB family and the basic metal.Specifically, this catalyzer can further include other additive and/or promotor, for example zinc or fluorochemical.Usually, the weight range of the promotor that is added is that several ppm are to several thousand ppm.
Support of the catalyst of the present invention mainly is an aluminum oxide, can also comprise some other additive in addition, for example silicon-dioxide, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, sodium oxide and calcium oxide.Usually, except aluminum oxide, the weight content of these oxide compounds is less than 50%, is preferably to be less than 10%, particularly preferably is, and this carrier only is made up of aluminum oxide and unavoidable impurities.As aluminum oxide, use be known aluminum oxide mutually or known partially hydrated aluminum oxide phase, for example α-, β-, γ-, δ-, θ-or x-aluminum oxide, boehmite, pseudobochmite or their mixture.
The shape of the employed carrier of catalyzer of the present invention can be granular, spherical, strip, ring-type, gear-like, extrudate, and is preferred spherical.The BET specific surface area of carrier is generally 200-350m
2/ g is preferably 220-320m
2/ g; Pore volume is generally 0.1-1.0ml/g, is preferably 0.2-0.8ml/g; Mean pore size is generally 4-40nm, is preferably 6-30nm, is preferably 20nm at the most especially.BET surface-area, pore volume and the pore size distribution of carrier can be optimized according to mode known in those skilled in the art.The used carrier of the present invention preferably before using at 300-800 ℃ of roasting 2-10 hour.
Catalyzer of the present invention prepares through the following steps: with the salpeter solution of the salt of the salpeter solution of the salt of I B-group metal and group VIII metal oxide impregnation alumina supporter once or in batches, flood the aqueous solution of alkali metal compound again; Drying is carried out in each step dipping back in 50-200 ℃ temperature range, carry out roasting in 250-650 ℃ temperature range.
The present invention preferably adopt each family's metal respectively the method for impregnated carrier prepare.The salpeter solution of the salt of the preferred I B-group metal of dipping earlier, flood the salpeter solution of the salt of group VIII metal again, the salt preferably nitrate of IB family and group VIII metal, the concentration of employed nitric acid will be enough to form clear solution at least, the pH value of solution is 0.1-3, is preferably 0.2-2; Final impregnating alkali metal compound solution, the solution of preferred oxyhydroxide, halogenide or nitrate, preferred especially hydroxide solution.The used volume of each step dipping solution is as the criterion to be no more than alumina supporter maximum absorption volume.Compound concentration in the solution is to calculate like this, and after this concentration should make dipping finish and impregnated carrier is converted into after the finished catalyst, the component that is deposited reaches desirable content in catalyzer.
After each step, dipping was finished, 50-200 ℃ of scope inner drying soaked carrier, be preferably 60-190 ℃, be preferably 70-180 ℃ especially.Drying continues to carry out, and till the water in the carrier after impregnated is removed basically fully, wants usually just can reach after the dry several hrs.Depend on the drying temperature that is adopted time of drying: temperature is high more, and time of drying is short more, usually between 1-20 hour.
In principle, dried catalyzer just can use, and can utilize hydrogen or hydrogen-containing gas to handle in hydrogenator, makes sedimentary metallic compound directly be reduced into metal.This catalyzer is preferably calcined after drying.Calcine mainly is the component that employed compound changed into be deposited or the parent of these components.Under the situation of utilizing metallic compound to flood, in calcination process, metallic compound mainly decomposes and generates metal and/or the metal oxide stay in the catalyzer.Calcining temperature in 200-650 ℃ of scope, is preferably 300-550 ℃ usually, is preferably 380-520 ℃ especially.Usually between 0.5-20 hour, calcination process preferably proceeds to many 15 hours to calcination time, especially preferably is at most 10 hours.Calcination process carries out in stove commonly used, for example in rotary tube furnace, carry out in tunnel oven or in retort furnace.Can after drying, directly calcine, needn't carry out intercooling dipping and dry carrier.
If necessary or desired, catalyzer after the calcining is in hydrogenator in the catalyzer use or before using, carry out the activated metal oxide compound and be reduced into metal, just make the oxide compound of group VIII metal and I B-group metal all be converted into metal.This process can be carried out under the hydrogenation situation automatically, or carries out in known manner.
The C5 fraction selective hydrogenation is normally carried out in gas/liquid phase process except that the process of alkynes, and wherein C5 fraction exists with liquid form, and hydrogen is present in the gas phase and/or is dissolved in the liquid phase.The setting of reaction conditions such as pressure, temperature, flow and hydrogen amount is a purpose to remove alkynes.Volume with catalyzer is a benchmark, and the liquid air speed of C5 fraction is 2-12m
3/ m
3* h, temperature is 30 ℃-70 ℃, pressure is 0.1MPa-4.0MPa, and the hydrogen that is added is benchmark to remove alkynes, to make C 5 diene loss minimum again, and the hydrogen amount that every mole of alkynes added is at least 1 mole, is preferably at least 2 moles, and be at most 30 moles, be preferably 20 moles at the most.
This method can perhaps be carried out in a plurality of parallel connections or placed in-line reactor in a reactor.
Catalyzer of the present invention has excellent catalytic performance, specifically, is to have higher activity, selectivity and long work-ing life in the process of the alkynes in the C5 fraction being carried out selective hydrogenation.
C5 fraction selective hydrogenation of the present invention removes the method for alkynes, can make that alkynes content is reduced to certain value in the material, and the loss of valuable diolefin component is less than 2%, this method is used for the C5 fraction separating technology, can shorten separation process, reduce cost of investment and energy consumption, reduce solvent loss.
Embodiment
Embodiment 1, preparation catalyzer 1
At ambient temperature, use salpeter solution (PH=1.0) oxide impregnation alumina supporter (the BET surface-area: 287m of cupric nitrate and Silver Nitrate
2/ g), drying is 4 hours under 120 ℃, calcines 4 hours down at 500 ℃ then, and take out and be cooled to room temperature; Use salpeter solution (PH=1.0) dipping of Palladous nitrate again, again drying and calcining; The aqueous solution with potassium hydroxide floods drying and calcining at last.The amount of dipping solution is the adsorbable maximum volume amount of employed carrier, and the setting of the concentration of metal compound solution should make catalyzer finally contain 3% bronze medal, 0.04% silver medal, 0.04% palladium and 0.3% potassium (all being weight percentage) in dipping solution.
Zhi Bei catalyzer is expressed as catalyzer 1 by this way.
Embodiment 2, preparation catalyzer 2
Repeat embodiment 1, change the setting of the concentration of metallic compound in the dipping solution, make catalyzer finally contain 6% bronze medal, 0.03% silver medal, 0.06% palladium and 0.6% potassium (all being weight percentage).
Zhi Bei catalyzer is expressed as catalyzer 2 by this way.
Embodiment 3, preparation catalyzer 3
Repeat embodiment 1, change the setting of the concentration of metallic compound in the dipping solution, make catalyzer finally contain 3% bronze medal, 0.03% silver medal, 0.03% palladium and 0.3% potassium (all being weight percentage).
Zhi Bei catalyzer is expressed as catalyzer 3 by this way.
Embodiment 4, preparation catalyzer C-1
At ambient temperature, at first use aqueous solution oxide impregnation alumina supporter (the BET surface-area: 287m of potassium hydroxide
2/ g), use aqueous nitric acid (PH=1.0) dipping of cupric nitrate and Silver Nitrate then, it is identical with embodiment 1 to use the aqueous nitric acid (PH=1.0) of Palladous nitrate to flood other conditions at last.
Zhi Bei catalyzer is expressed as catalyzer C-1 by this way.
Embodiment 5, preparation catalyzer C-2
At ambient temperature, at first use salpeter solution (PH=1.0) oxide impregnation alumina supporter (the BET surface-area: 287m of Palladous nitrate
2/ g) use the aqueous nitric acid (PH=1.0) of cupric nitrate and Silver Nitrate to flood then, with the aqueous solution dipping of potassium hydroxide, other conditions are identical with embodiment 1 at last.
Zhi Bei catalyzer is expressed as catalyzer C-2 by this way.
Embodiment 6, preparation catalyzer C-3
Repeat embodiment 1, the setting of the concentration of metallic compound in the dipping solution should make catalyzer finally contain 10% bronze medal, 0.3% silver medal, 0.3% palladium and 3% potassium (all being weight percentage).
Zhi Bei catalyzer is expressed as catalyzer C-3 by this way.
Embodiment 7, preparation catalyzer C-4
Repeat embodiment 1, the setting of the concentration of metallic compound in the dipping solution should make catalyzer finally contain 0.8% bronze medal, 0.1% silver medal, 0.005% palladium and 0.05% potassium (all being weight percentage).
Zhi Bei catalyzer is expressed as catalyzer C-4 by this way.
Embodiment 8, preparation catalyzer C-5
Adopting the BET specific surface area is 366m
2The aluminum oxide of/g is a carrier, repeats embodiment 1.
Zhi Bei catalyzer is expressed as catalyzer C-5 by this way.
Embodiment 9, preparation catalyzer C-6
Adopting the BET specific surface area is 180m
2The aluminum oxide of/g is a carrier, repeats embodiment 1.
Zhi Bei catalyzer is expressed as catalyzer C-6 by this way.
Embodiment 10, selective hydrogenation
In using the testing apparatus of fixed-bed reactor, the alkynes in the isoprene is carried out selective hydrogenation evaluate catalysts 1,2,3 and the catalytic performance of catalyzer C-1, C-2, C-3, C-4, C-5, C-6 relatively.With 99.8% (wt) isoprene material, wherein contain 950ppm alkynes (2-butyne and valylene) and hydrogen and mix the back by beds, pressure all adopts 0.8MPa, joining the hydrogen in the C5 fraction and the mol ratio of alkynes is 11, and temperature of reaction is that 40 ℃, the liquid air speed of material are 8m
3/ m
3* h.Utilize material after the gas chromatographic analysis selective hydrogenation.
Each activity of such catalysts and selective evaluation the results are shown in table 1.
Table 1 evaluating catalyst result
| Catalyzer | Load component concentration Cu/Ag/Pd/K (%) | Carrier specific surface (m 2/g) | The preparation method | Initial reaction stage | Continuous operating time (hr) | Reaction terminating | ||
| Alkynes (ppm) | IP rate of loss (%) | Alkynes content (ppm) | IP rate of loss (%) | |||||
| 1 | 3/0.04/0.04/0.3 | 287 | Cu-Ag/Pd/K | 38 | 1.4 | 600 | 39 | 1.2 |
| 2 | 6/0.03/0.06/0.6 | 287 | Cu-Ag/Pd/K | 29 | 1.5 | 600 | 30 | 1.5 |
| 3 | 3/0.03/0.03/0.3 | 287 | Cu-Ag/Pd/K | 44 | 1.3 | 600 | 44 | 1.3 |
| C-1 | 3/0.04/0.04/0.3 | 287 | K/Cu-Ag/Pd | 33 | 1.7 | 41 | 94 | 1.5 |
| C-2 | 3/0.04/0.04/0.3 | 287 | Pd/Cu-Ag/K | 75 | 1.5 | 64 | 101 | 1.9 |
| C-3 | 10/0.3/0.3/3 | 287 | Cu-Ag/Pd/K | 8 | 3.4 | 30 | 42 | 2.8 |
| C-4 | 0.8/0.1/0.005/0.05 | 287 | Cu-Ag/Pd/K | 87 | 1.9 | 28 | 121 | 1.4 |
| C-5 | 3/0.04/0.04/0.3 | 366 | Cu-Ag/Pd/K | 30 | 1.8 | 72 | 64 | 1.5 |
| C-6 | 3/0.04/0.04/0.3 | 180 | Cu-Ag/Pd/K | 69 | 1.1 | 72 | 73 | 1.1 |
Annotate: Cu-Ag/Pd/K represents to use earlier copper silver mixing solutions oxide impregnation alumina supporter among the preparation method, uses the palladium solution impregnation again, floods with potassium hydroxide solution at last.The rest may be inferred for alternate manner.Catalyzer 1,2,3 600 hours catalytic performances of operation does not continuously have considerable change.
Compare each catalyzer, the Preparation of catalysts method has most important property to the catalytic performance of catalyzer, different preparation methods can produce significantly influence to activity of such catalysts, selectivity and life-span, and preparation method of the present invention is effective to Preparation of Catalyst of the present invention; The load component of catalyzer and content thereof with scope of the present invention for well; Support of the catalyst also affects the catalytic performance of catalyzer, is good with carrier of the present invention.
Claims (10)
1. a selective hydrogenation catalyst is characterized in that, this catalyzer is carrier with the aluminum oxide, is benchmark with the gross weight of catalyzer, and in weight content, comprise following component: the I B-group metal at least a periodic table of elements, its content are 1%-8%; Group VIII metal at least a periodic table of elements, its content are 0.01%-0.2%; At least a basic metal, its content are 0.1%-2%;
And this catalyzer can prepare by following method: at first use the salpeter solution oxide impregnation alumina supporter of the salt of the salpeter solution of salt of I B-group metal and group VIII metal, then with the aqueous solution dipping of alkali metal compound; Drying is carried out in each step dipping back in 50-200 ℃ temperature range, carry out roasting in 250-650 ℃ temperature range.
2. catalyzer as claimed in claim 1 is wherein used the salpeter solution step impregnation alumina supporter successively of the salt of the salpeter solution of salt of I B-group metal and group VIII metal.
3. catalyzer as claimed in claim 1, the pH value scope of the salpeter solution of the salt of the salpeter solution of the salt of wherein said I B-group metal and group VIII metal is 0.1-3.
4. catalyzer as claimed in claim 1, the pH value scope of the salpeter solution of the salt of the salpeter solution of the salt of wherein said I B-group metal and group VIII metal is 0.2-2.
5. catalyzer as claimed in claim 1, the salt of wherein said I B-group metal and group VIII metal is nitrate.
6. catalyzer as claimed in claim 1, wherein said alkali metal compound are the oxyhydroxide of this metal.
7. catalyzer as claimed in claim 1, wherein load components contents is respectively: I B-group metal accounts for 2%-6%, and VIII family metal accounts for 0.01%-0.1%, and basic metal accounts for 0.2%-1%.
8. catalyzer as claimed in claim 1, wherein I B-group metal is at least a in copper and the silver, wherein copper accounts for 90% of I B-group metal at least; The group VIII metal is a palladium; Basic metal is potassium.
9. catalyzer as claimed in claim 1, the specific surface area of wherein said carrier are 200-350m
2/ g.
10. catalyzer as claimed in claim 1 carries out selective hydrogenation to the unsaturated compound in the C5 fraction method, this method is to carry out in mutually in gas phase or gas-liquid, its temperature range is 30 ℃-70 ℃, and its pressure range is 0.1MPa-4.0MPa, and liquid air speed is 2-12m
3/ m
3.h, hydrogen flowing quantity makes the C5 fraction loss not mostly be benchmark again to remove undesirable unsaturated hydrocarbons.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011360437A CN1188494C (en) | 2001-09-29 | 2001-09-29 | Selective hydrogenation catalyst and its preparation method and application |
| TW091122409A TW583178B (en) | 2001-09-29 | 2002-09-27 | Process for separating C5 cuts obtained from a petroleum cracking process |
| US10/255,628 US6958426B2 (en) | 2001-09-29 | 2002-09-27 | Process for separating C5 cuts obtained from a petroleum cracking process |
| KR1020020059101A KR100869156B1 (en) | 2001-09-29 | 2002-09-28 | Process for separating c5 cuts obtained from a petroleum cracking process |
| JP2002286554A JP4346294B2 (en) | 2001-09-29 | 2002-09-30 | Method for separating C5 fractions obtained from petroleum cracking process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011360437A CN1188494C (en) | 2001-09-29 | 2001-09-29 | Selective hydrogenation catalyst and its preparation method and application |
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| CN1410515A CN1410515A (en) | 2003-04-16 |
| CN1188494C true CN1188494C (en) | 2005-02-09 |
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| CN105771984B (en) * | 2014-12-25 | 2019-09-03 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst for carbon five fraction and preparation method thereof |
| CN106588554A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Method for removing alkynes from C5 fraction |
| CN106622255A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst as well as preparation method and application thereof |
| CN114433129B (en) * | 2020-10-20 | 2024-02-13 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof, and method for selectively hydrogenating alkyne |
| CN114160161B (en) * | 2021-12-24 | 2023-05-26 | 中国科学院过程工程研究所 | Pt-Fe bimetallic catalyst for CO and NO oxidation and preparation method and application thereof |
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