CN101850250A - selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof - Google Patents
selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof Download PDFInfo
- Publication number
- CN101850250A CN101850250A CN 200910131988 CN200910131988A CN101850250A CN 101850250 A CN101850250 A CN 101850250A CN 200910131988 CN200910131988 CN 200910131988 CN 200910131988 A CN200910131988 A CN 200910131988A CN 101850250 A CN101850250 A CN 101850250A
- Authority
- CN
- China
- Prior art keywords
- quality
- carrier
- catalyst
- magnesium
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a selective hydrogenation catalyst for removing alkadiene in mixed C4, which consists of carrier and the following active components measured with the carrier as a reference: 0.1 to 2.0 percent by weight of Pd and 0.1 to 1.0 percent by weight of Pb; the carrier is alumina, the surface layer of which is covered by magnesia-alumina spinel, and the carrier contains 5 to 15 percent by weight of the magnesia-alumina spinel. The catalyst is used for the selective hydrogenation of alkadiene, and has the advantages of high activity and selectivity, high sulphur resistance and long service life.
Description
Technical field
The present invention be a kind of from monoolefine the Catalysts and its preparation method of selective hydrogenation and removing diene impurity wherein, specifically, be a kind of from the mixed c 4 fraction Catalysts and its preparation method of selective hydrogenation and removing alkadienes.
Background technology
At present, the clean gasoline demand increases day by day, and alkylate oil has become the ideal composition of reformulated gasoline because of its steam forces down, octane number height, sensitiveness are little, do not contain alkene and aromatic hydrocarbons.Component after the most of butadiene of the mixed c 4 extracting that raw material for alkylation generally adopts the steam cracking process to produce perhaps adopts plant catalytic mixed c 4 that cracking is produced and mixed c 4 etherificate remaining ingredient afterwards.The butadiene that generally contains 0.3～1.2 quality % in the raw material for alkylation.In alkylated reaction, butadiene can generate the higher acid soluble oil of relative molecular mass (ASO), causes the quality of alkylate oil to descend, and the reaction acid consumption increases (every 1Kg butadiene increases sulfuric acid consumption 13.4Kg).The preferred approach that now addresses this problem is that the butadiene in the raw material is removed in selective hydrogenation, part 1-butylene in the raw material can turn to the 2-butylene by isomery simultaneously, thereby improve the octane number of alkylate oil, this is because the butene alkylated product of 2-is high by 2～3 than 1-butylene octane number.
As everyone knows, Metal Palladium is the optimum activity component of selectively hydrogenating butadiene, and palladium catalyst has been widely used in the alkynes that removes in monoolefine or the diolefin fraction and the diolefin in the monoolefine fraction.In raw material for alkylation, contain iso-butane, normal butane, anti-butylene, n-butene, isobutene, maleic, butadiene etc. usually, the hydrogenation and removing butadiene, be the 2-butylene with the 1-isomerization of butene simultaneously, generally select the Pd catalyst for use, but, be one of major reason that causes the unsaturated hydrocarbons oligomerisation reaction because Pd itself has acidity.People have carried out a series of improvement at the shortcoming of Pd single-metal reforming catalyst.
USP3531545, USP4132745, USP3772440 propose to add the sulfide passivation catalyst in raw material, reduce activity of such catalysts, but catalyst still needs in 163～190 ℃ of reactions of higher temperature, be unfavorable for that the 1-isomerization of butene is the thermodynamical equilibrium of 2-butylene, thereby influenced the isomerization rate of 1-butylene.Therefore the second metal promoted catalyst component improves catalyst activity and Study on Selectivity is more and more with adding, but most of second metal promoted catalyst component is Ag, Cu, Au, Cr, Sn, Zn etc.A kind of catalyst and method for making of the C4 of being used for selective hydrogenation of diolefin as raw material for alkylation are disclosed as CN1084222C, this patent is a principal phase at δ mutually, contain simultaneously that supported palladium and golden component make catalyst on the mixed phase alumina support of α, θ phase, be used for the refinery alkylation raw material and take off butadiene, have reaction effect preferably.
CN1107547C discloses a kind of selective hydrocatalyst, by alumina support be distributed in the palladium and at least a tin or the plumbous M metal component of being selected from of carrier granular periphery, characteristics M metal component is included in the particle volume between particle periphery and the depth 500 μ m.This catalyst can make the hydrogenation speed of butadiene be higher than the hydrogenation speed of 1-butylene.
Adopt alkali-metal fluoride KF to modify Al among the USP5489565
2O
3Carrier makes the Pd-Ag bimetallic catalyst, selects the hydrogenation result to show that catalyst has good activity stability.
At present, the carrier of the industrial selection hydrogenation catalyst that generally adopts is aluminium oxide and silica.But the acid site of aluminium oxide or silica surface is easily caused unsaturated hydrocarbons generation oligomerisation and is generated " green oil ", causes activity of such catalysts and selectivity to descend.For addressing this problem, people set about improving catalyst performance from support modification and interpolation cocatalyst component.EP0839573A1 loads on palladium and silver on the low acid spinel carrier such as being selected from zinc aluminate, magnesium aluminate or magnesium titanate and makes catalyst, and this catalyst has excellent catalytic activity and ethylene hydrogenation selectivity.
CN02130795.4 discloses a kind of light hydrocarbon distillate selective dediene catalyst and preparation method, this catalyst comprises active component palladium and the carrier magnesium aluminum oxide solid solution of 0.05～1.0 heavy %, and magnesium/al mole ratio is 1.0～12.0 in the described magnesium aluminum oxide solid solution.Not only there is acid centre on this magnesium/aluminium solid solution surface, also there is an amount of basic center, this basic center can increase the double-bond shift activity of catalyst to alkene, and can make in the raw material for alkylation more 1-isomerization of butene is the 2-butylene, helps to improve the octane number of alkylate oil.The metal promoter that this catalyst adds is selected from cobalt, molybdenum, nickel or tungsten.
Summary of the invention
The catalyst and the preparation method that the purpose of this invention is to provide alkadienes in a kind of selective hydrogenation and removing mixed c 4, this catalyst has higher activity, selectivity and sulfur poisoning-resistant ability, and has good service life.
The catalyst of alkadienes comprises carrier and is the following active component of content that benchmark calculates with the carrier in the selective hydrogenation and removing mixed c 4 provided by the invention:
Pd 0.1～2.0 quality %,
Pb 0.01～1.0 quality %,
Described carrier is the aluminium oxide that the top layer covers magnesium aluminate spinel, and wherein the content of magnesium aluminate spinel is 5～15 quality %.
The present invention has the low acid magnesium aluminate spinel (MgAl of skim with the surface
2O
4) aluminium oxide be carrier, load active component Pd and auxiliary agent Pb make catalyst.This method for preparing catalyst is simple, can improve the selectivity of butadiene hydrogenation in the C-4-fraction, effectively prolongs the service life of catalyst, and catalyst stability is good, and the reaction bed temperature is difficult for raising fast (temperature runaway).
The specific embodiment
The present invention's magnesium salt solution impregnated alumina makes the top layer and covers magnesium aluminate spinel (MgAl after high-temperature roasting
2O
4) alumina support, and then with the carrier that makes earlier with containing palladium compound solution dipping introducing palladium, introduce lead after drying, the roasting again and make catalyst.The specific area that this catalyst is less, bigger pore volume, and the auxiliary agent lead of introducing can make prolong the service life of catalyst, and improve alkadienes conversion ratio, selectivity and the anti-sulphur ability of catalyst.
Carrier of the present invention is the aluminium oxide of surface coverage magnesium aluminate spinel, preferably contains the magnesium aluminate spinel of 5～12 quality % in the carrier.The shape of described aluminium oxide can be sphere, strip gear, sheet, cloverleaf pattern, column or graininess, and is preferred spherical.The preferred gama-alumina of described aluminium oxide, the specific area of gama-alumina are 250～450m
2/ g, pore volume are 0.25～0.85ml/g.
The specific area of described carrier is 75～150m
2/ g, preferred 80～120m
2/ g, pore volume are 0.25～0.5ml/g, preferred 0.30～0.48ml/g.
The metal component that catalyst of the present invention contains is palladium and lead, and its content is that benchmark calculates preferred 0.1～0.5 quality % of the content of Pd, preferred 0.01～0.3 quality % of the content of Pb with the carrier.
Preparation of catalysts method of the present invention comprises carrier of the present invention with the water-soluble solution impregnation that contains palladium compound, uses the water-soluble lead compound solution impregnation again, dry then, roasting after dry, the roasting.
In the said method, the preparation method of carrier is: flood gama-alumina with magnesium salt solution, preferred 20～45 ℃ of dipping temperature, Gu during dipping liquid/than being 0.6～1.2ml/g, the solid that obtains behind the dipping makes carrier in 900～1100 ℃ of roastings after drying.Described baking temperature is 60～150 ℃, preferred 80～120 ℃, and be 2～16 hours, preferred 4～12 hours drying time, and roasting time is 2～20 hours, preferred 2～10 hours.
Described magnesium salts is magnesium chloride, magnesium nitrate or magnesium sulfate, preferred magnesium nitrate.The concentration of described magnesium salt solution is 0.5～30 quality %, preferred 1～20 quality %.
The method that the present invention prepares catalyst is earlier with the water-soluble solution impregnating carrier that contains palladium compound, the described preferred palladium nitrate of palladium compound, acid chloride, palladium acetylacetonate or palladium bichloride, the more preferably palladium bichloride of containing.When adopting palladium bichloride, in solution, adds proper inorganic acid earlier before the dipping, make maceration extract be acid and make the palladium bichloride dissolving, Gu during dipping liquid/than being 0.4～1.0ml/g, dipping temperature is 20～45 ℃.After containing the palladium compound solution impregnated carrier, be dried the carrier that the back roasting obtains introducing palladium.
The carrier of introducing palladium is flooded with water-soluble lead compound solution again, the preferred plumbi nitras of described water-soluble lead compound, Gu during dipping liquid/than being 0.4～1.0ml/g, dipping temperature is 20～45 ℃, will flood afterwards solid drying after roasting obtain catalyst.
Said method is introduced 80～200 ℃ of the described baking temperatures of metal component, time in carrier be 5～20 hours.Described sintering temperature is 300～700 ℃, preferred 400～500 ℃, preferred 1～8 hour of roasting time.
Catalyst of the present invention is applicable to the selective hydrogenation and removing alkadienes wherein before the raw material for alkylation subtractive process, the preferred mixed c 4 of described raw material for alkylation, wherein olefin(e) centent is that 20～45 quality %, butadiene content are that 0.01～1.0 quality %, surplus are butane substantially, in addition, also contain trace impurities such as sulphur.Catalyst of the present invention needs with hydrogen or hydrogen-containing gas before use 100～550 ℃ of reduction, preferred 0.5～4.0 hour of recovery time.
Using catalyst of the present invention is 45～110 ℃, preferred 50～90 ℃ to the temperature that mixed c 4 carries out removing alkadiene by selective hydrogenation, pressure is 0.4～3.0MPa, preferred 1.0～2.5MPa, hydrogen/alkadienes mol ratio is 1.0～8.0, preferred 2.0～5.0, the liquid volume air speed of charging during reaction is 0.5～10h
-1, preferred 2.0～6.0h
-1
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare catalyst of the present invention.
(1) preparation carrier
Getting the 1kg specific area is 316m
2/ g, pore volume are the gama-alumina bead (Shandong Baichuan Huitong Chemical Science and Technology Co., Ltd.'s production) of 0.65ml/g, are the Mg (NO of 10 quality % with 800ml concentration
3)
2Solution was in 25 ℃ of dippings 20 minutes, and dipping back solid is in 120 ℃ of dryings 4 hours, again in 950 ℃ of roastings 8 hours, and making specific area is 118m
2/ g, pore volume are the carrier of 0.45ml/g, wherein MgAl
2O
4Content be 5.7 quality %.
(2) preparation catalyst
Get the PdCl of 5.67g
2With concentration is the HCl dissolving of 37 quality %, joins and makes the PdCl that concentration is 0.012 quality % in the deionized water
2Solution 480ml.The carrier that (1) step makes is put into PdCl
2In 25 ℃ of dippings 2 hours, dipping back solid was in 80 ℃ of dryings 12 hours in the solution, 450 ℃ of roastings 4 hours.
Solid after the above-mentioned roasting is contained 0.8g Pb (NO with 480ml
3)
2Solution impregnation 2 hours, 120 ℃ of dryings 6 hours, 450 ℃ of roastings 6 hours, catalyst A, wherein be that the Pd content that benchmark calculates is that 0.2 quality %, Pb content are 0.05 quality % with the carrier.
Example 2
Method by example 1 prepares catalyst, and different is (1) step to use Mg (NO
3)
2Behind the solution impregnation gama-alumina bead, drying was 1100 ℃ of roastings 10 hours, and making specific area is 80m
2/ g, pore volume are the carrier of 0.31ml/g, wherein MgAl
2O
4Content 5.7 quality %.Method by 1 (2) step of example prepares catalyst then, wherein is that the Pd content that benchmark calculates is that 0.2 quality %, Pb content are 0.05 quality % with the carrier.
Example 3
Method by 1 (1) step of example prepares carrier, and that different is the Mg (NO that is used to flood the gama-alumina bead
3)
2The concentration of solution is 15 quality %, and obtaining specific area after dipping back solid drying, the roasting is 118m
2/ g, pore volume are the carrier of 0.45ml/g, wherein MgAl
2O
4Content 8.5 quality %.
Get 8.51g PdCl
2Powder dissolves with HCl, adds deionized water and makes the PdCl that concentration is 0.017 quality %
2Solution 480ml.The above-mentioned carrier that makes is put into PdCl
235 ℃ of dippings 4 hours, dipping back solid was in 80 ℃ of dryings 12 hours in the solution, 450 ℃ of roastings 4 hours.Contain 0.8g Pb (NO with 480ml then
3)
2Solution impregnation 2 hours, 110 ℃ of dryings 8 hours, 500 ℃ of roastings 6 hours obtain catalyst C, wherein are that the Pd content that benchmark calculates is that 0.3 quality %, Pb content are 0.05 quality % with the carrier.
Example 4
Method by 1 (1) step of example prepares carrier, and that different is the Mg (NO that is used to flood the gama-alumina bead
3)
2The concentration of solution is 20 quality %, and obtaining specific area after dipping back solid drying, the roasting is 118m
2/ g, pore volume are the carrier of 0.45ml/g, wherein MgAl
2O
4Content 11.0 quality %.
Get 5.67g PdCl
2Powder dissolves with HCl, adds deionized water and makes the PdCl that concentration is 0.012 quality %
2Solution 480ml.The above-mentioned carrier that makes is put into PdCl
225 ℃ of dippings 2 hours, dipping back solid was in 80 ℃ of dryings 12 hours in the solution, 450 ℃ of roastings 4 hours.Contain 1.6g Pb (NO with 480ml then
3)
2Solution impregnation 6 hours, 120 ℃ of dryings 12 hours, 450 ℃ of roastings 6 hours obtain catalyst D, wherein are that the Pd content that benchmark calculates is that 0.2 quality %, Pb content are 0.1 quality % with the carrier.
Comparative Examples
Getting the 1kg specific area is 316m
2/ g, pore volume are the gama-alumina bead (Shandong Baichuan Huitong Chemical Science and Technology Co., Ltd.'s production) of 0.65ml/g, 4 hours, 950 ℃ roastings of 200 ℃ of dryings 6 hours, and making specific area is 123m
2/ g, pore volume are the Al of 0.46ml/g
2O
3Carrier.
Method by 1 (2) step of example prepares catalyst, and making with the carrier is that the Pd content that benchmark calculates is that 0.2 quality %, Pb content are the catalyst of 0.05 quality %, is designated as catalyst E.
Example 5～9
Following example is used to estimate the reactivity worth of catalyst of the present invention.
On the micro anti-evaluation device of laboratory, filling 10g catalyst is warming up to 150 ℃, feeds hydrogen reducing 16 hours.With the mixed c 4 is raw material, and it consists of: isobutene 38 quality %, 1-butylene 2.1 quality %, butadiene 0.5 quality %, sulfur content 30ppm, all the other are iso-butane.At 1.6MPa, 50 ℃, liquid volume air speed is 6.0h
-1, hydrogen/alkadienes mol ratio is to carry out selective hydrogenation under 3.0 the condition, the results are shown in Table 1.
Table 1
| Instance number | The catalyst numbering | Butadiene conversion, quality % | The monoolefine yield, quality % |
| ??5 | ??A | ??99.0 | ??99.8 |
| ??6 | ??B | ??97.5 | ??99.5 |
| ??7 | ??C | ??100 | ??98.2 |
| Instance number | The catalyst numbering | Butadiene conversion, quality % | The monoolefine yield, quality % |
| ??8 | ??D | ??98.8 | ??99.4 |
| ??9 | ??E | ??96.0 | ??94.6 |
Example 10
On the micro anti-evaluation device of laboratory, filling 10g catalyst C is a raw material with the mixed c 4, and it consists of: isobutene 38 quality %, 1-butylene 2.1 quality %, butadiene 0.5 quality %, sulfur content 61ppm, all the other are iso-butane.At 1.5MPa, 60 ℃, liquid volume air speed is 4.0h
-1, hydrogen/alkadienes mol ratio is to carry out selective hydrogenation under 5.0 the condition, butadiene conversion is 100%, catalyst selectivity, promptly the monoolefine yield is 99.6 quality %.
Example 11
On the micro anti-evaluation device of laboratory, filling 10g catalyst A is a raw material with the mixed c 4, and it consists of: isobutene 38 quality %, 1-butylene 2.1 quality %, butadiene 0.5 quality %, sulfur content 102ppm, all the other are iso-butane.At 1.6MPa, 50 ℃, liquid volume air speed is 6.0h
-1, hydrogen/alkadienes mol ratio is to carry out selective hydrogenation under 2.0 the condition, butadiene conversion is 99.2 quality %, the monoolefine yield is 99.6 quality %.
Example 10 and 11 result show that when the sulfur content in the raw material increased to 61ppm and 102ppm by 30ppm, activity of such catalysts and selectivity were influenced hardly, illustrate that catalyst of the present invention has sulfur poisoning-resistant ability preferably.
Example 12
Get 10g catalyst C, pack in the reaction tube of internal diameter φ 8mm, long 800mm, mixed c 4 after the desulfurization of employing catalytic cracking unit is a reaction raw materials, and raw material consists of: iso-butane 54.325 quality %, isobutene 39.25 quality %, 1-butylene 1.86 quality %, butadiene 0.325 quality %, anti-butene-2 1.89 quality %, maleic-20.68 quality %, normal butane 1.67 quality %, sulfur content 91ppm.At 1.5MPa, 55 ℃, liquid volume air speed is 10h
-1, hydrogen/alkadienes mol ratio is successive reaction 1500 hours under 4.0 the condition, butadiene conversion is 100%, the monoolefine yield is 98.8 quality %.Reaction result shows that catalyst of the present invention has stability preferably.
Claims (10)
1. the catalyst of alkadienes in the selective hydrogenation and removing mixed c 4 comprises carrier and is the following active component of content that benchmark calculates with the carrier:
Pd 0.1～2.0 quality %,
Pb 0.01～1.0 quality %,
Described carrier is the aluminium oxide that the top layer covers magnesium aluminate spinel, and wherein the content of magnesium aluminate spinel is 5～15 quality %.
2. according to the described catalyst of claim 1, it is characterized in that described Pd content is 0.1～0.5 quality %, Pb content is 0.01～0.3 quality %, and described aluminium oxide is a gama-alumina.
3. according to the described catalyst of claim 1, the content that it is characterized in that magnesium aluminate spinel in the described carrier is 5～12 quality %.
4. according to the described catalyst of claim 1, the specific area that it is characterized in that carrier is 75～150m
2/ g, pore volume are 0.25～0.5ml/g.
5. described Preparation of catalysts method of claim 1 comprises described carrier with the water-soluble solution impregnation that contains palladium compound, uses the water-soluble lead compound solution impregnation again, dry then, roasting after dry, the roasting.
6. in accordance with the method for claim 5, it is characterized in that described carrier is to flood gama-alumina with magnesium salt solution, dry back makes in 900～1100 ℃ of roastings.
7. in accordance with the method for claim 6, it is characterized in that described magnesium salts is magnesium chloride, magnesium nitrate or magnesium sulfate.
8. in accordance with the method for claim 6, the concentration that it is characterized in that described magnesium salt solution is 1～20 quality %.
9. in accordance with the method for claim 5, it is characterized in that the described water-soluble palladium compound that contains is palladium nitrate, acid chloride, palladium acetylacetonate or palladium bichloride.
10. in accordance with the method for claim 5, it is characterized in that described water-soluble lead compound is a plumbi nitras.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910131988 CN101850250A (en) | 2009-03-31 | 2009-03-31 | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910131988 CN101850250A (en) | 2009-03-31 | 2009-03-31 | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101850250A true CN101850250A (en) | 2010-10-06 |
Family
ID=42802031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910131988 Pending CN101850250A (en) | 2009-03-31 | 2009-03-31 | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101850250A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125878A (en) * | 2011-01-11 | 2011-07-20 | 中国石油大学(北京) | Modified Al2O3 carrier and preparation method thereof |
| CN102580751A (en) * | 2011-01-11 | 2012-07-18 | 中国石油大学(北京) | Diene selectivity hydrogenation catalyst and preparation method thereof |
| CN106881125A (en) * | 2017-03-17 | 2017-06-23 | 钦州学院 | A kind of catalyst and preparation method for diene hydrogenation |
| CN107398273A (en) * | 2016-05-19 | 2017-11-28 | 财团法人工业技术研究院 | Catalyst and process for hydrogenating cyclobutanedione compounds |
| CN110201680A (en) * | 2019-07-04 | 2019-09-06 | 山西师范大学 | It is a kind of for alpha, beta-unsaturated aldehyde/ketone selective hydrogenation catalyst, preparation method and catalysis process |
| CN112675837A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Carbon four selective hydrogenation catalyst, preparation method and application thereof |
-
2009
- 2009-03-31 CN CN 200910131988 patent/CN101850250A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125878A (en) * | 2011-01-11 | 2011-07-20 | 中国石油大学(北京) | Modified Al2O3 carrier and preparation method thereof |
| CN102580751A (en) * | 2011-01-11 | 2012-07-18 | 中国石油大学(北京) | Diene selectivity hydrogenation catalyst and preparation method thereof |
| CN102125878B (en) * | 2011-01-11 | 2012-11-14 | 中国石油大学(北京) | Modified Al2O3 carrier and preparation method thereof |
| CN107398273A (en) * | 2016-05-19 | 2017-11-28 | 财团法人工业技术研究院 | Catalyst and process for hydrogenating cyclobutanedione compounds |
| CN107398273B (en) * | 2016-05-19 | 2019-12-24 | 财团法人工业技术研究院 | Catalyst and process for hydrogenating cyclobutanedione compounds |
| CN106881125A (en) * | 2017-03-17 | 2017-06-23 | 钦州学院 | A kind of catalyst and preparation method for diene hydrogenation |
| CN110201680A (en) * | 2019-07-04 | 2019-09-06 | 山西师范大学 | It is a kind of for alpha, beta-unsaturated aldehyde/ketone selective hydrogenation catalyst, preparation method and catalysis process |
| CN110201680B (en) * | 2019-07-04 | 2022-10-04 | 山西师范大学 | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde/ketone, preparation method and catalysis method |
| CN112675837A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Carbon four selective hydrogenation catalyst, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101434508B (en) | Acetylene hydrocarbon selective hydrogenation method | |
| CN101428228B (en) | Selective hydrogenation catalyst and method of producing the same | |
| CN101850250A (en) | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof | |
| CN106582706B (en) | Selective hydrogenation of butadiene catalyst | |
| CN101898131B (en) | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof | |
| CN103769078A (en) | Low carbon alkane dehydrogenation catalyst for alkene production and its preparation method and application | |
| CN104588011B (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN106582625A (en) | Catalyst for selective hydrogenation of butadiene | |
| CN101081362B (en) | Carrier containing magnalium complexes and method for preparing the same | |
| CN101898130B (en) | Method for preparing dehydrogenation catalyst | |
| CN102553632B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof and application | |
| CN102441444A (en) | Preparation method of dehydrogenation catalyst | |
| CN103586046A (en) | Catalyst for preparing light olefins from synthetic gas and preparation method thereof | |
| CN101348406B (en) | Hydrogenation method for cracking hydrocarbon having nine carbon atoms or more | |
| CN101850997A (en) | Method for preparing spherical alumina | |
| CN101940928B (en) | Nickel-based catalyst for hydroisomerization of n-butene for preparing butene-2 or butene-1 | |
| CN100484625C (en) | Diene selection hydrogenation catalyst, and preparation method | |
| CN108014832A (en) | The hydrogenation technique of C-2-fraction in selective hydrogenation catalyst and its application and preparing ethylene by steam cracking | |
| CN107952472A (en) | A kind of alkyl aromatic hydrocarbon isomerization catalyst and preparation and application | |
| CN107952471A (en) | Alkyl aromatic hydrocarbon isomerization catalyst and preparation and application | |
| CN102441400A (en) | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas | |
| CN110841650B (en) | Non-noble metal catalyst for selective hydrogenation and olefin removal of reformate, and preparation method and application thereof | |
| CN108067228B (en) | Propane dehydrogenation catalyst and preparation method thereof | |
| CN103418379B (en) | Remove the Catalysts and its preparation method of alkadienes in carbon four | |
| CN104549247A (en) | Hydrocarbon material selective hydrogenation catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20101006 |