CN1827746A - Selective hydrogenation catalyst and preparation method thereof - Google Patents
Selective hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN1827746A CN1827746A CN 200510008984 CN200510008984A CN1827746A CN 1827746 A CN1827746 A CN 1827746A CN 200510008984 CN200510008984 CN 200510008984 CN 200510008984 A CN200510008984 A CN 200510008984A CN 1827746 A CN1827746 A CN 1827746A
- Authority
- CN
- China
- Prior art keywords
- carrier
- silicon oxide
- catalyzer
- weight
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Disclosed are a selective hydrogenation catalyst and its process for preparing, in which the said catalyst contains a carrier and effective dose of hydrogenating active metal components loaded on the carrier, and the said catalyst is an aluminum oxide having a mix crystal phase with one or some of the delta, theta and alpha phase and containing silicon oxide, selecting the carrier as benchmark, the silicon oxide content of the said carrier is 1-40 mass %. The process for preparing the said carrier consists of mixing, modeling and roasting an aluminum oxide having a mix crystal phase with one or some of the delta, theta and alpha phase with silicon oxide and/or precursor of silicon oxide at a sintering temperature of 350-800 DEG C for 1-12 hours of calcining. In relation to the present catalyst, using the catalyst provided by this invention in selective hydrogenation dedialkene, the active and the selective are improved.
Description
Technical field
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, more particularly relate to a kind of selective hydrogenation catalyst of removing with method of hydrotreating diolefine and preparation method thereof that is used for.
Background technology
The raw materials used mixed C that produces from catalytic cracking unit usually of sulfuric acid process in the refinery (or hydrofluoric acid method) alkyl plant
4Cut, wherein contained Trimethylmethane and alkene generate the isoparaffin mixture under the acid effect, be the desirable blend component of high-quality stop bracket gasoline.But, in raw material for alkylation, containing the diolefin about 0.5 volume % usually, these diolefins or generate corresponding ester with acid-respons increase acid consumption, or polymerization generates heavy alkylate, and the yield of light alkylate oil is reduced.When adopting solid acid catalyst to carry out alkylation, diolefin is easier of the catalyst surface polymerization, causes catalyst deactivation to reduce its work-ing life.In addition, also contain in such as petroleum productss such as pyrolysis gasolines just like diolefine and alkyl alkenyl arene equal altitudes unsaturated hydrocarbons, the easy polymerization reaction take place of these hydro carbons generates the gelatinize compound, thereby makes product oil nature variation.
In the presence of hydrogenation catalyst, can effectively diolefine be removed by selective hydrogenation.Wherein, containing the palladium noble metal catalyst is well the custom catalysts of removing alkadiene by selective hydrogenation because of its active height, selectivity.
Patent CN1071443A discloses a kind of one-stage selective hydrogenation of gasoline splitting catalyzer that is used for, and this catalyzer is supported precious metal palladium and constituted by δ, α mixing crystal formation aluminum oxide.Containing the problem that the catalyzer of single Pd metal exists is to sulfur sensitive, the poor stability of catalyzer when handling the higher stock oil of sulphur content.
CN1107704C discloses a kind of selective hydrogenation catalyst for pyrolysis gasoline, this catalyzer is by δ, α mixed type alumina load precious metal palladium, active ingredient is eggshell type at carrier surface and distributes, with δ, α mixed type alumina supporter is benchmark, the content of palladium is 0.05-0.4 weight %, and the add-on of basic metal and/or alkaline-earth metal is 0.05-2.0 weight %, and the support of the catalyst pore volume is 0.5-0.9ml/g, wherein the hole of 40-200 accounts for more than 85% of total hole volume, and specific surface is 70-140m
2/ g, alpha-crystal form accounts for 0.1-5% in the alumina supporter.In addition, this catalyzer also load helps active ingredient, helps active ingredient to be selected from a kind of in the VIB of the periodic table of elements or the IB family element, and the weight ratio that helps active ingredient and Pd metal is 0.2-2: 1.Help the existence of active ingredient favourable to the distribution that improves the Pd metal, alkali-metal existence can make the acid reduction of carrier surface, can reduce and give birth to the deposition of charcoal material on catalyst surface in the reaction process, thereby the performance of catalyzer is improved.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of new activity and selectivity better choice hydrogenation catalyst and preparation method thereof.
Catalyzer provided by the invention contains a kind of carrier and loads on the hydrogenation active metals component of significant quantity on this carrier, wherein, described carrier is to have one or more aluminum oxide that mix crystalline phases and contain silicon oxide among δ, θ and the α, with the carrier is benchmark, and the content of silicon oxide is 1-40 weight % in the described carrier.
Method provided by the invention comprises a kind of carrier of preparation and introduce the hydrogenation active metals component of significant quantity in this carrier, wherein, the preparation method of described carrier is precursor mixing, moulding and the roasting with a kind of aluminum oxide and a kind of silicon oxide and/or silicon oxide, with the carrier is benchmark, the content of silicon oxide is 1-40 weight % in the described carrier, described aluminum oxide is to have one or more aluminum oxide that mix crystalline phases and contain silicon oxide among δ, θ and the α, described maturing temperature is 350-800 ℃, roasting time 1-12 hour.
Compare with existing catalyzer, the active of the diolefine selective hydrogenation of catalyzer provided by the invention obviously improves.
For example, under identical reaction conditions, be the C of 0.35 volume % to a kind of butadiene content
4When raw material for alkylation carried out selective hydrogenation, when adopting catalyzer provided by the invention (is carrier loaded 0.29 weight % and 0.75 weight % with the aluminum oxide that contains 8 weight % silicon oxide), divinyl can be reduced to 185ppm in the product; And when adopting reference catalyst, divinyl only can be reduced to 512ppm in the product.
Embodiment
According to catalyzer provided by the invention, be benchmark with described carrier, the content of silicon oxide is preferably 5-30 weight %, more preferably 8-25 weight % in the described carrier.The mixture of one or more metals in the preferred at least a nickel of described hydrogenation activity component, platinum, palladium or nickel, platinum, palladium and the group formed by molybdenum, vanadium, cobalt, tungsten, zinc, more preferably palladium and molybdenum, the hydrogenation activity component concentration, in oxide compound and with the catalyzer is that benchmark is preferably the heavy % of 0.1-15, the heavy % of further preferred 0.1-5.
According to method provided by the invention, described moulding can be carried out according to a conventional method, for example, can be with described aluminum oxide mix with the precursor of silicon oxide and/or silicon oxide, the method preparation of extruded moulding and roasting.Wherein, described have that one or more mix the aluminum oxide of crystalline phases among δ, θ and the α, can be that commercially available commodity also can be by any one known method preparation.For example, by pseudo-boehmite is being enough to make it become the method preparation of roasting under the aluminum oxide condition with one or more mixing crystalline phases among δ, θ and the α mutually.Pseudo-boehmite is converted into have δ, one or more conditions of mixing the aluminum oxide of crystalline phases are well known in the art among θ and the α, for example, maturing temperature is 900-1200 ℃, roasting time is 1-10h.Preferred maturing temperature is 1000-1100 ℃, and roasting time is 2-8h.The precursor of described silicon oxide and/or silicon oxide is preferably the precursor of silicon oxide, and the precursor of silicon oxide can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in water medium forms silicon gel, colloidal sol.In the preferred compounds such as water glass, silicon sol, silicon gel and silicon ester wherein one or more.Further preferred silicon sol wherein.When adopting the moulding of extrusion method, carry out smoothly for guaranteeing extrusion, when extrusion moulding, can add an amount of extrusion aid and/or tackiness agent, extrusion moulding then.The kind of described extrusion aid, tackiness agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.The temperature of described roasting is preferably 400-600 ℃, and roasting time is preferably 2-8 hour.
One or more alumina supporters that mix crystalline phases and contain silicon oxide among the described δ of having, θ and the α have conventional specific surface and pore volume with one or more mixed crystal phase alumina among δ, θ and the α, and preferential specific surface is a 30-160 rice
2/ gram, more preferably 50-110 rice
2/ gram, preferred pore volume is 0.3-0.7 milliliter/gram, more preferably 0.4-0.6 milliliter/gram.
The invention provides the Preparation of catalysts method is included in the hydrogenation active metals component that is enough to significant quantity and is deposited under the condition on the described aluminum oxide that contains silicon oxide, the aluminum oxide that will contain silicon oxide contacts with the solution that contains the hydrogenation active metals compound, for example by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process.
When the method that adopts dipping was introduced the hydrogenation active metals component, the preparation of described dipping solution and dipping method were ordinary method.Wherein, by adjusting and control to concentration, consumption or the described carrier consumption of dipping solution, the method for preparing specified metal content catalyzer is conventionally known to one of skill in the art.
Catalyzer provided by the invention has higher hydrogenation activity, selectivity and stability to the diolefine in the gasoline fraction oil, be particularly suitable for containing diolefine gasoline fraction oil be the hydrofining of purpose with the hydrogenation dialkene removal.Described gasoline fraction can be catalytically cracked gasoline, coker gasoline, straight-run spirit, pressure gasoline etc.
The following examples will the invention will be further described.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Embodiment 1
3000 gram powdery pseudo-boehmites (Chang Ling refinery catalyst plant is produced, and aluminum oxide butt content is 70 weight %) are placed muffle furnace,, rise to 1025 ℃, keep reducing to room temperature naturally after 6 hours, obtain aluminum oxide A with the heat-up rate of 10 ℃/min
1X-ray diffraction method is measured aluminum oxide A
1Crystalline phase.Through comparing with the JCPDS card, wherein the d value is 1.396,1.986,2.460 and 2.730 and δ phase alumina; 1.390,2.850,2.720,2.430 and 2.010 and θ phase alumina; 2.085 2.552,1.601 and 3.479 are corresponding with alpha-phase aluminum oxide.Aluminum oxide A
1Have δ, θ and α and mix crystalline phase.
Get aluminum oxide A
11900 grams are with 550 gram silicon sol (Haiyang Chemical Plant, Qingdao's product, silica content 30 weight %, sodium oxide content 0.4 weight %) mix, it is the cloverleaf pattern bar of 1.4mm that extrusion becomes external garden diameter, and wet bar was in 120 ℃ of dryings 6 hours, 600 ℃ of roastings 5 hours obtain support of the catalyst S
1, wherein dioxide-containing silica is 8 weight %.
Take by weighing 0.254 gram analytical pure Palladous chloride, be dissolved in the 66ml distilled water, be mixed with palladium chloride solution.Take by weighing 60 gram carrier S
1, with palladium chloride solution dipping 2h.Dipping back is 120 ℃ dried overnight, then 500 ℃ roasting 3 hours.The solution impregnation 2 hours that contains 0.562 gram ammonium molybdate again with 66ml, wet bar be 120 ℃ dried overnight, 500 ℃ roasting 3 hours, obtains catalyzer C then
1Catalyzer C
1Middle metal Pd O and MoO
3Content be respectively 0.29 weight % and 0.75 weight %.
Comparative Examples 1
With 3000 gram powdery pseudo-boehmites (with embodiment 1), it is the cloverleaf pattern bar of 1.4mm that extrusion becomes external garden diameter, and wet bar is in 120 ℃ of dryings 6 hours, then, place muffle furnace,, rise to 1025 ℃ with the heat-up rate of 10 ℃/min, keep reducing to room temperature naturally after 6 hours, obtain aluminum oxide S
2X-ray diffraction method is measured aluminum oxide S
2Crystalline phase.Through comparing with the JCPDS card, wherein the d value is 1.396,1.986,2.460 and 2.730 and δ phase alumina; 1.390,2.850,2.720,2.430 and 2.010 and θ phase alumina; 2.085 2.552,1.601 and 3.479 are corresponding with alpha-phase aluminum oxide.Aluminum oxide S
2Have δ, θ and α and mix crystalline phase.
Take by weighing 0.254 gram analytical pure Palladous chloride, be dissolved in the 66ml distilled water, be mixed with palladium chloride solution.Take by weighing 60 gram carrier S
2, with palladium chloride solution dipping 2h.Dipping back is 120 ℃ dried overnight, then 500 ℃ roasting 3 hours.The solution impregnation 2 hours that contains 0.562 gram ammonium molybdate again with 66ml, wet bar be 120 ℃ dried overnight, 500 ℃ roasting 3 hours, obtains catalyzer D then
1Catalyzer D
1Middle metal Pd O and MoO
3Content be respectively 0.29 weight % and 0.75 weight %.
Embodiment 2
Method by embodiment 1 prepares catalyzer C
2, the Palladous chloride consumption was 0.205 gram when different was the first step dipping, ammonium molybdate content is 1.702 grams in the second step steeping fluid.Catalyzer C
2Middle metal Pd O and MoO
3Content be respectively 0.23 weight % and 2.25 weight %.
Embodiment 3
Method by embodiment 1 prepares catalyzer C
3, the Palladous chloride consumption was 0.313 gram when different was the first step dipping, the ammonium molybdate consumption was 3.460 grams when second step flooded.Catalyzer C
3Middle metal Pd O and MoO
3Content be respectively 0.35 weight % and 4.50 weight %.
Embodiment 4
3000 gram powdery pseudo-boehmites (with embodiment 1) are placed muffle furnace,, rise to 1050 ℃, keep reducing to room temperature naturally after 5 hours, obtain aluminum oxide A with the heat-up rate of 10 ℃/min.X-ray diffraction method is measured aluminum oxide A
2Crystalline phase.Through comparing with the JCPDS card, wherein the d value is 1.396,1.986,2.460 and 2.730 and δ phase alumina; 1.390,2.850,2.720,2.430 and 2.010 and θ phase alumina; 2.085 2.552,1.601 and 3.479 are corresponding with alpha-phase aluminum oxide.Aluminum oxide A
2Have δ, θ and α and mix crystalline phase.
Get aluminum oxide A
21800 grams mix with 1059 gram silicon sol (with embodiment 1), and it is the cloverleaf pattern bar of 1.4mm that extrusion becomes external garden diameter, and wet bar is in 120 ℃ of dryings 5 hours, and 500 ℃ of roastings 3 hours obtain support of the catalyst S
3, wherein dioxide-containing silica is 15 weight %.
Take by weighing 0.415 gram analytical pure Palladous chloride, be dissolved in the 66ml distilled water, be mixed with palladium chloride solution.Take by weighing 60 gram carrier S
3, with palladium chloride solution dipping 2h.Dipping back is 120 ℃ dried overnight, then 450 ℃ roasting 3 hours.The solution impregnation 2 hours that contains 1.720 gram ammonium molybdates again with 66ml, wet bar be 120 ℃ dried overnight, 450 ℃ roasting 3 hours, obtains catalyzer C then
4Catalyzer C
4Middle metal Pd O and MoO
3Content be respectively 0.46 weight % and 2.25 weight %.
Embodiment 5
With 3000 the gram powdery pseudo-boehmites (with embodiment 1) place muffle furnace, with the heat-up rate of 10 ℃/min, rise to 1070 ℃, kept 3 hours, reduce to room temperature naturally after, obtain aluminum oxide A
3X-ray diffraction method is measured aluminum oxide A
3Crystalline phase.Through comparing with the JCPDS card, wherein the d value is 1.396,1.986,2.460 and 2.730 and δ phase alumina; 1.390,2.850,2.720,2.430 and 2.010 and θ phase alumina; 2.085 2.552,1.601 and 3.479 are corresponding with alpha-phase aluminum oxide.Aluminum oxide A
3Have δ, θ and α and mix crystalline phase.
Get aluminum oxide A 1800 gram, mix with 1692 gram silicon sol (with embodiment 1), it is the cloverleaf pattern bar of 1.4mm that extrusion becomes external garden diameter, and wet bar is in 120 ℃ of dryings 3 hours, and 400 ℃ of roastings 4 hours obtain support of the catalyst S
4, wherein dioxide-containing silica is 22 weight %.
Take by weighing 0.615 gram analytical pure Palladous chloride, be dissolved in the 66ml distilled water, be mixed with palladium chloride solution.Take by weighing 60 gram carrier S
4, with palladium chloride solution dipping 2h.Dipping back is 120 ℃ dried overnight, then 420 ℃ roasting 3 hours.The solution impregnation 2 hours that contains 0.566 gram ammonium molybdate again with 66ml, wet bar be 120 ℃ dried overnight, 420 ℃ roasting 3 hours, obtains catalyzer C then
5Catalyzer C
5Middle metal Pd O and MoO
3Content be respectively 0.69 weight % and 0.75 weight %.
Embodiment 6-10
The performance of present embodiment explanation catalyzer of the present invention.
Respectively with 10 milliliters of catalyzer C that sieve through the 16-20 eye mesh screen
1-C
5Be contained in 10 milliliters of small stationary bed bioreactors, earlier catalyzer reduced under nitrogen atmosphere before the reaction, reduction temperature is 400 ℃, hydrogen dividing potential drop 2MPa, and 6 hours recovery times, switch to reaction raw materials then, the raw material composition sees Table 1.Temperature of reaction is 60 ℃, pressure 1.8MPa, air speed 6h
-1, H
2/ divinyl ratio is 1.2.Sampling analysis after 24 hours is carried out in reaction, and the product compositional analysis carries out on the TRACE 2000 type chromatographic instruments that Thermo Electron company produces.Wherein, and divinyl in the product (1,3-C
4H
6) content list in the table 2.
Monoolefine yield=(in the raw material in monoolefine content/product monoolefine content) * 100%.
Comparative Examples 2
The performance of this Comparative Examples explanation reference catalyst.
According to estimating reference catalyst D with embodiment 6 identical methods
1, the results are shown in Table 2.
Table 1
| Component | Content v% |
| C 3H 8 | 0.03 |
| Iso-C 4H 10 | 53.48 |
| n-C 4H 10 | 2.26 |
| n-C 4H 8 | 15.93 |
| iso-C 4H 8 | 25.98 |
| tran-2-C 4H 8 | 1.63 |
| cis-2-C 4H 8 | 0.32 |
| 1，3-C 4H 6 | 0.35 |
| n-C 5H 12 | 0.02 |
| Total sulfur ppm | 35.0 |
| Water-content ppm | 141.2 |
Table 2
| Embodiment | Catalyzer | Butadiene content/ppm | Monoolefine yield/% |
| 6 | C 1 | 185 | 100.3 |
| Comparative Examples 2 | D 1 | 512 | 100.1 |
| 7 | C 2 | 170 | 100.2 |
| 8 | C 3 | 175 | 100.2 |
| 9 | C 4 | 90 | 100.2 |
| 10 | C 5 | 85 | 100.1 |
By table 2 as seen, catalyzer provided by the invention is keeping the high optionally while, and activity obviously improves.
Claims (9)
1, a kind of selective hydrogenation catalyst, this catalyzer contains a kind of carrier and loads on the hydrogenation active metals component of significant quantity on this carrier, wherein, described carrier is to have one or more aluminum oxide that mix crystalline phases and contain silicon oxide among δ, θ and the α, with the carrier is benchmark, and the content of silicon oxide is 1-40 weight % in the described carrier.
2, catalyzer according to claim 1 is characterized in that, is benchmark with the carrier, and the content of silicon oxide is 5-30 weight % in the described carrier.
3, catalyzer according to claim 2 is characterized in that, the content of silicon oxide is 8-25 weight % in the described carrier.
4, catalyzer according to claim 1, it is characterized in that, described hydrogenation active metals component be selected from least a nickel, platinum, palladium or nickel, platinum, palladium and the group formed by molybdenum, vanadium, cobalt, tungsten, zinc in the mixture of one or more metals, in oxide compound and with the catalyzer is benchmark, and the hydrogenation active metals components contents is the heavy % of 0.1-15.
5, catalyzer according to claim 4 is characterized in that, described hydrogenation activity component is palladium and molybdenum, is benchmark in oxide compound and with the catalyzer, and the hydrogenation active metals components contents is the heavy % of 0.1-5.
6, the described Preparation of catalysts method of claim 1, this method comprises a kind of carrier of preparation and introduce the hydrogenation active metals component of significant quantity in this carrier, wherein, the preparation method of described carrier is precursor mixing, moulding and the roasting with a kind of aluminum oxide and a kind of silicon oxide and/or silicon oxide, with the carrier is benchmark, the content of silicon oxide is 1-40 weight % in the described carrier, described aluminum oxide is that one or more mix the aluminum oxide of crystalline phase among having δ, θ and α, described maturing temperature is 350-800 ℃, roasting time 1-12 hour.
7, method according to claim 6 is characterized in that, the precursor of described silicon oxide is selected from one or more in water glass, silicon sol and the silicon ester, is benchmark with the carrier, and the content of silicon oxide is 5-30 weight % in the described carrier.
8, method according to claim 7 is characterized in that, the precursor of described silicon oxide is a silicon sol, and the content of silicon oxide is 8-25 weight % in the described carrier.
9, method according to claim 6 is characterized in that, described maturing temperature is 400-600 ℃, roasting time 2-8 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100089849A CN100510020C (en) | 2005-02-28 | 2005-02-28 | Selective hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100089849A CN100510020C (en) | 2005-02-28 | 2005-02-28 | Selective hydrogenation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827746A true CN1827746A (en) | 2006-09-06 |
| CN100510020C CN100510020C (en) | 2009-07-08 |
Family
ID=36946302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100089849A Active CN100510020C (en) | 2005-02-28 | 2005-02-28 | Selective hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100510020C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757818A (en) * | 2011-04-29 | 2012-10-31 | 中国石油化工股份有限公司 | Sulfur-free gasoline production method |
| CN103418379A (en) * | 2012-05-24 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for removing alkadiene in C4 and preparation method thereof |
| CN110385133A (en) * | 2019-07-22 | 2019-10-29 | 四川蜀泰化工科技有限公司 | A kind of pre-converting catalyst and preparation method thereof |
-
2005
- 2005-02-28 CN CNB2005100089849A patent/CN100510020C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757818A (en) * | 2011-04-29 | 2012-10-31 | 中国石油化工股份有限公司 | Sulfur-free gasoline production method |
| CN102757818B (en) * | 2011-04-29 | 2015-07-01 | 中国石油化工股份有限公司 | Sulfur-free gasoline production method |
| CN103418379A (en) * | 2012-05-24 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for removing alkadiene in C4 and preparation method thereof |
| CN103418379B (en) * | 2012-05-24 | 2015-10-28 | 中国石油化工股份有限公司 | Remove the Catalysts and its preparation method of alkadienes in carbon four |
| CN110385133A (en) * | 2019-07-22 | 2019-10-29 | 四川蜀泰化工科技有限公司 | A kind of pre-converting catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100510020C (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1130265C (en) | Catalyst capable of using on carrier in organic compound conversion reaction | |
| CN111514924B (en) | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon | |
| KR20030061372A (en) | A catalyst for selective hydrogenating unsaturated hydrocarbon, and a preparation and an application of the same | |
| CZ267994A3 (en) | Catalysts, process of their preparation and use | |
| CN101664688B (en) | Hydrogenation desilicification catalyst and preparation thereof | |
| CN1927461A (en) | Heteropoly acid containing hydrocracking catalyst and its preparation method | |
| CN105080592A (en) | Aromatic olefin-reducing catalyst and use thereof | |
| CN102451694A (en) | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof | |
| CN101898138B (en) | Method for preparing vulcanized dehydrogenation catalyst | |
| CN112191268A (en) | Ni-IL/mesoporous aluminum oxide catalyst and preparation and application thereof | |
| CN1084224C (en) | Catalyst for dehydrogenation of saturated hydrocarbon and preparation thereof | |
| CN102910997A (en) | Method for preparing olefins by using dehydrogenation of light alkanes with sulfur-containing substances added in raw materials | |
| CN87101513A (en) | Dehydrogen of saturated hydrocarbon platinum, tin, lithium, sulfur catalyst | |
| CN100510020C (en) | Selective hydrogenation catalyst and preparation method thereof | |
| CN101348406A (en) | Hydrogenation method for cracking hydrocarbon having nine carbon atoms or more | |
| WO2001003829A1 (en) | Selective hydrogenation catalyst system, its preparation and usage | |
| CN104588008A (en) | Saturated alkane dehydrogenation catalyst and preparation method thereof | |
| US9611435B2 (en) | Method for selective hydrogenation of unsaturated compound | |
| CN1048425C (en) | Catalyst and method for converting heavy arene into light one | |
| CN1351110A (en) | Process for presulfurizing hydrocatalyst | |
| JPH0529504B2 (en) | ||
| CN104492450A (en) | Coked gasoline desilication catalyst and preparation method thereof | |
| CN1351111A (en) | Process for presulfurizing hydrocatalyst | |
| CN1160747A (en) | Preparation of reforming platinum-rhenium catalyst | |
| CN1039592C (en) | Process for producing hydrogenating catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |