CN1181164C - Method for preparing polymetallic reforming catalyst - Google Patents
Method for preparing polymetallic reforming catalyst Download PDFInfo
- Publication number
- CN1181164C CN1181164C CNB02121588XA CN02121588A CN1181164C CN 1181164 C CN1181164 C CN 1181164C CN B02121588X A CNB02121588X A CN B02121588XA CN 02121588 A CN02121588 A CN 02121588A CN 1181164 C CN1181164 C CN 1181164C
- Authority
- CN
- China
- Prior art keywords
- carrier
- heavy
- catalyst
- lanthanide series
- series metal
- 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.)
- Expired - Lifetime
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a preparing method for a multimetallic reforming catalyst. The catalyst comprises platinum with the weight percentage of 0.1 to 2.0%, rhenium with the weight percentage of 0.1 to 2.0%, chloride with the weight percentage of 0.2 to 3.0%, lanthanide series metal or yttrium with the weight percentage of 0.01 to 2.0%, and an inorganic high temperature resistant oxide carrier. The preparing method comprises that water soluble compounds which contains the platinum, the rhenium, the lanthanide series metal or the yttrium, and the chloride are prepared into immersion liquids, and the quantity of the immersion liquids is from 1.1 to 5.0 times as much as the saturation adsorption volume of the carrier. Under the conditions of the pressure of 0.001 to 0.08MPa and rotation, the carrier is dipped to be dried and roasted. The method can cause multimetallic components to be uniformly distributed in the catalyst, and thereby, the activity and the selectivity of the catalyst are improved.
Description
Technical field
The present invention is a kind of preparation method of multimetal reforming catalyst.Specifically, be a kind of method for preparing the multimetal reforming catalyst of platiniferous, rhenium.
Background technology
Platinum-rhenium reforming catalyst becomes one of catalyzer that is most widely used in the full scale plant with its excellent activity that has and stability.But platinum-rhenium reforming catalyst still has some deficits, and mainly is that the rhenium constituent element has stronger hydrogenolysis activity.Compare with the continuous reforming process that adopts platinum-tin catalyst, semi-regenerative reforming process liquid product yield and the hydrogen purity of using platinum-rhenium catalyst are lower, and promptly the selectivity of platinum-rhenium catalyst is relatively poor.Therefore, under the prerequisite that keeps the platinum-rhenium catalyst good stability, improving selectivity of catalyst is the developing direction of semi-regenerative reforming catalyzer.
Improving optionally a kind of method of platinum-rhenium reforming catalyst is to introduce the 3rd or the 4th metal constituent element as auxiliary agent in platinum-rhenium reforming catalyst, and these auxiliary agents can suppress the hydrogenolysis activity of rhenium constituent element, thereby improve selectivity of catalyst.Use the 3rd more metal constituent element to be selected from rare earth element, as USP3,776,860 disclose a kind of platinum-rhenium reforming catalyst that contains rare earth element, and its rare earth element of selecting for use is praseodymium, neodymium, samarium or ytterbium, and its content is 0.1～5.0 heavy %.This patent adopts co-impregnation, and the preferred saturated legal system of soaking altogether is equipped with catalyzer.
In the prior art, the dipping method of multicomponent reforming catalyst adopts saturated pickling process more, promptly presses the saturated adsorption capacity of carrier, preparation equal volume dipping solution amount, that contain required each constituent element desired amount, carrier is placed solution, static dipping certain hour, oven dry then.USP 3,776, and 860 is the platinum-rhenium reforming catalyst that preferred this method preparation contains the rare earth constituent element.This method adds the difference of each constituent element characterization of adsorption because carrier does not have " immersion " in solution, causes different constituent elements can't fully move, exchange mutually at the carrier body, is difficult to guarantee that each constituent element is at carrier body phase uniform distribution.Because reforming reaction is not subjected to diffusion control basically, active component means the minimizing of catalyzer effective active position in the uneven distribution of carrier body phase.On the other hand, because steeping process is an immobilized, the mass transfer exchange that is adsorbed medium-catalyst metal constituent element between the bed of material of different adsorption concentrations is poor, causes the adsorptive capacity of the bed of material activated metal component of different positions to there are differences again.
The dipping method of the another kind of preparation multimetal reforming catalyst of using always soaks-filter method altogether, is about to carrier impregnation in the dipping solution that contains activated metal component and halogen, puts the certain hour after-filtration only, drying.All adopt this method as CN1147536A, CN1160747A.This method is vied each other in steeping process because there is the difference of characterization of adsorption in each constituent element, and mutual restraining effect, result are that every kind of constituent element adsorption efficiency descends, and the content of metal constituent element is lower than actual charging capacity in the catalyzer.For the precious metal reforming catalyst, mean that will produce qualified catalyzer need increase the platinum consumption, cause production cost to increase.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of multimetal reforming catalyst, the catalyst metal constituent element of this method preparation is evenly distributed, and has good activity and selectivity.
The inventive method is with the steeping fluid impregnated carrier time, adopt the mode of decompression and rotation to flood, make the solvent in the steeping fluid in steeping process, constantly volatilize, impregnation concentration constantly increases, energy of rotation enhancement steeping fluid in the steeping process contacts with carrier, promotes active ingredient uniform distribution in carrier.Therefore, the catalyzer that makes of the inventive method has higher activity and selectivity.
Description of drawings
Fig. 1, Fig. 2 are the catalyst metal constituent element radial distribution figure of the inventive method preparation.
Fig. 3, Fig. 4 are comparative catalyst's metal constituent element radial distribution figure.
Embodiment
The preparation method of multimetal reforming catalyst provided by the invention comprises that the water-soluble cpds with platiniferous, rhenium, lanthanide series metal or yttrium, chlorine is mixed with steeping fluid, the amount of steeping fluid is 1.1～5.0 times of carrier saturated adsorption capacity, impregnated carrier under 0.001～0.08MPa and rotating conditions, roasting then.Described catalyzer comprises platinum, the rhenium of 0.1～2.0 heavy %, the chlorine of 0.2～3.0 heavy %, 0.01～2.0 heavy % lanthanide series metal or yttrium and the inorganic high-temperature resistant oxide carrier of 0.1～2.0 heavy %.
The inventive method is applicable to the preparation of multimetal reforming catalyst, is specially adapted to contain the preparation of the platinum-rhenium reforming catalyst of the 3rd metal constituent element.Described preferred lanthanide series metal of the 3rd metal constituent element or yttrium, as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the preferred ytterbium of lanthanide series metal, samarium or neodymium.The content of the 3rd metal constituent element preferred 0.1～1.0 heavy %.
Described support of the catalyst is a refractory oxide, preferred aluminum oxide, more preferably γ-Al
2O
3Or η-Al
2O
3The carrier that uses during dipping should be in type.The type shape of carrier can be sphere, bar shaped, cylindrical, trilobal or quatrefoil.Forming method can adopt the conventional methods such as ball, spin, compressing tablet, extrusion of dripping to carry out.
The present invention adopts vacuum rotational method impregnated carrier to prepare catalyzer, promptly under decompression operation, required metal component is mixed with steeping fluid by the content requirement in the catalyzer, the amount of this steeping fluid should be greater than the carrier saturated adsorption capacity, so that steeping fluid energy submergence carrier, the amount of steeping fluid is preferably 1.1～3.0 times of carrier saturated adsorption capacity.Dip operation is preferably carried out in rotary vacuum evaporator, and concrete working method is: add steeping fluid in rotary vacuum evaporator, pour carrier again into, be evacuated to required pressure, preferred pressure is 0.005～0.05MPa.Then, limit heating edge rotation.Heating temperature is that dipping temperature is 20～80 ℃, and preferred 30～80 ℃, more preferably 40～60 ℃, speed of rotation should not be too fast, and rotational line speed is 0.01～1.0 meter per second, preferred 0.05～0.5 meter per second, more preferably 0.05～0.3 meter per second.Preferred 1～8 hour of dipping time, more preferably 2～4 hours.
Behind the vacuum rotary dipping, moisture evaporates substantially in the steeping fluid, and catalyzer is drying regime, can directly carrier be taken out this moment and carry out roasting, also carrier can be taken out back roasting again after further drying under the normal pressure.Described drying temperature is 80～160 ℃, preferred 90～120 ℃.Under reduced pressure carry out the preferred 0.01～0.08MPa of exsiccant pressure.
Described maturing temperature is 400～700 ℃, and preferred 450～550 ℃, roasting time is 2～12 hours, and the volume ratio of control dry air and catalyzer is 500～1200 during roasting.Catalyzer after the roasting will reduce, and reducing gas can be selected hydrogen or carbon monoxide for use, preferred hydrogen.Gas agent volume ratio is 500～1200 during reduction, and temperature is 400～550 ℃, and the time is 2～12 hours.
The platinic compound of selecting for use during the preparation steeping fluid that contains comprises Platinic chloride, platinous chloride and various platinum chlorine complex ion, as Pt (NH
3)
4 2+, preferred Platinic chloride.Contain rhenium compound and be selected from perrhenic acid, rhenium carbonyl, preferred perrhenic acid.The nitrate or the muriate of the preferred lanthanide series metal of compound of lanthanide series metal, the more preferably nitrate of ytterbium, samarium or neodymium or muriate.The compound that contains yttrium is selected from Yttrium trinitrate or Yttrium trichloride.
The another kind of constituent element of described catalyzer is a chlorine.Chlorine can be introduced in catalyst preparation process, also can in the catalyzer use, introduce, best mode be the form of or Organohalogen compounds inorganic with hydrochloric acid or other when dipping and other metal constituent element together introduce.
The catalyzer of the present invention's preparation must pass through prevulcanized before use.Prevulcanized can be by injecting H in hydrogen stream
2The mode of S or other organic or inorganic sulfide is carried out, and the sulphur content on the catalyzer is 0.01～2.00 heavy %, preferred 0.04～0.40 heavy %.
Catalyzer of the present invention is applicable to that boiling range is 40～230 ℃ and (presses GB 255 methods analysts, as follows) virgin naphtha or comprise that the boiling range of explained hereafter such as coking in the refining of petroleum, cracking is the reformation of 40～230 ℃ petroleum naphtha, be specially adapted to the reformation of virgin naphtha.
Below by example in detail the present invention, but the present invention is not limited to this.
Comparative Examples 1～4
Adopt dipping-filtration method to prepare multimetallic catalyst.
Get 60 gram bar shaped γ-Al
2O
3Carrier (Fushun catalyst plant), its saturated adsorption capacity is 58 milliliters, with the nitrate of Platinic chloride, perrhenic acid, yttrium or the rare earth metal of predetermined amount and the steeping fluid that hydrochloric acid is made into 108 milliliters, contain Pt 0.22 heavy %, Re 0.5 heavy %, an amount of yttrium or rare earth metal, Cl 1.8 heavy % (all with respect to the butt alumina weight) in this steeping fluid, 24 hours after-filtration of dipping under the room temperature, 120 ℃ of dryings 12 hours, 500 ℃, gas agent volume ratio are roasting in 700 o'clock 4 hours in the dry air, H
2In 480 ℃, gas agent volume ratio be reduction in 500 o'clock 4 hours, make catalyzer.The used nitrate of each example and the metal content of concentration and catalyzer see Table 1 in the preparation process.
Comparative Examples 5～8
Press USP 3,776,860 method, the promptly saturated legal system of soaking altogether is equipped with Pt-Re-RE/ γ-Al
2O
3Catalyzer.
Get 60 gram bar shaped γ-Al
2O
3Carrier, its saturated adsorption capacity is 58 milliliters, with the nitrate of Platinic chloride, perrhenic acid, yttrium or the rare earth metal of predetermined amount and the steeping fluid that hydrochloric acid is made into 58 milliliters, make wherein to contain Pt 0.22%, Re 0.48%, rare earth metal or yttrium, Cl 1.6% (all with respect to the butt alumina weight), steeping fluid is 0.75 with the carrier bulk ratio.Dipping is 24 hours under the room temperature, 120 ℃ of dryings 12 hours, and 500 ℃, gas agent volume ratio are roasting in 700 o'clock 4 hours in the dry air, H
2In 480 ℃, gas agent volume ratio be reduction in 500 o'clock 4 hours, make catalyzer.The used nitrate of each example and the metal content of concentration and catalyzer see Table 1 in the preparation process.
Example 1～4
Prepare catalyzer with the inventive method.
Get 60 gram γ-Al
2O
3Carrier, its saturated adsorption capacity is 58 milliliters, Platinic chloride, perrhenic acid, Yttrium trinitrate and hydrochloric acid with predetermined amount are made into 82 milliliters of steeping fluids, wherein contain Pt 0.22%, Re 0.48%, Cl 1.8% and an amount of yttrium or rare earth metal (with respect to the butt alumina weight), steeping fluid is 1.2 with the carrier bulk ratio.Carrier and steeping fluid are poured in 500 ml flasks, on rotary vacuum evaporator, flooded.Control condition is: 0.02MPa, 50 ℃, rotational line speed 0.05 meter per second.Dipping and drying are finished after 2 hours.Taking out solid, is roasting in 700 o'clock 4 hours with its 500 ℃, gas agent volume ratio in dry air, H
2In 480 ℃, gas agent volume ratio be reduction in 500 o'clock 4 hours, make catalyzer.The used nitrate of each example and the metal content of concentration and catalyzer see Table 1 in the preparation process.
As shown in Table 1, the metal constituent element content of the catalyst A-3 of the inventive method preparation, B-3, C-3, D-3 is near charging capacity.And the catalyst A-1, B-1, C-1, the D-1 metal constituent element content that make with common dipping-filtration method will be lower than charging capacity.
Example 5
Metal constituent element content to the catalyst A-2 of the catalyzer of the inventive method preparation and control methods preparation, B-2, C-2, D-2 carries out replicate analysis.Randomly draw three groups of samples at the different sites of each catalyst sample, analyze metal content, the results are shown in Table 2.
As shown in Table 2, catalyst metal content data good reproducibility of the present invention illustrates that the catalyst metal constituent element is evenly distributed between carrier layer.And, metal constituent element skewness between carrier layer is described with comparative catalyst's metal content data poor repeatability of saturated immersion process for preparing.
Example 6
The metal constituent element of the catalyzer of the catalyzer of the inventive method preparation and control methods preparation distributed at carrier body section mutually compare.
Go up the section of metal constituent element on carrier of measuring among catalyst A-3, B-3, comparative catalyst A-2, the B-2 at electron microprobe examination (EPM-810Q type, day island proper Tianjin company produces) and distribute, the result sees Fig. 1～4 respectively.X-coordinate is the carrier profile diameter among the figure, is arbitrary unit, and ordinate zou is a count value, represents metal constituent element distribution density.
The result of Fig. 1～4 shows, the catalyst A-3 of the inventive method preparation, the metal constituent element of B-3 are even along the carrier radial distribution, and the platinum constituent element of comparative catalyst A-2, B-2 is " eggshell type " and distributes, and rare earth yttrium or ytterbium are " yolk type " and distribute.
Example 7
This example is estimated catalyzer of the present invention and comparative catalyst.
The catalyst A-3 of the inventive method preparation and comparative catalyst A-2 catalyzer are contained in 420 ℃, hydrogen stream under the condition of hydrogen sulfide of 0.10 heavy % (relative catalyzer) and carry out sulfidizing.On 10 milliliters of devices, be that raw material is estimated with straight-run spirit then, appreciation condition is: 0.98MPa, hydrogen/hydrocarbon volume ratio 1200: 1, feed volume air speed 2.0h
-1, 490 ℃, 510 ℃ of temperature.Feedstock property sees Table 3, and evaluation result sees Table 4.
Example 8
Method by example 7 is estimated catalyst B-3 and B-2.Different is that experimental installation is 100 milliliters of middle-scale devices, and hydrogen/hydrocarbon volume ratio is 800: 1, and evaluation result sees Table 4.
Table 1
| Instance number | The catalyzer numbering | Rare earth compound | Metal content in the catalyzer, heavy % | |||
| Title | Concentration, heavy % | Pt | Re | RE | ||
| Comparative Examples 1 | A-1 | Yttrium trinitrate | 0.8 | 0.17 | 0.35 | 0.29 |
| Comparative Examples 2 | B-1 | Ytterbium nitrate | 0.5 | 0.15 | 0.34 | 0.22 |
| Comparative Examples 3 | C-1 | Samaric nitrate | 0.2 | 0.16 | 0.33 | 0.19 |
| Comparative Examples 4 | D-1 | Neodymium nitrate | 0.3 | 0.12 | 0.32 | 0.18 |
| Comparative Examples 5 | A-2 | Yttrium trinitrate | 0.8 | 0.22 | 0.46 | 0.79 |
| Comparative Examples 6 | B-2 | Ytterbium nitrate | 0.5 | 0.21 | 0.47 | 0.49 |
| Comparative Examples 7 | C-2 | Samaric nitrate | 0.2 | 0.22 | 0.47 | 0.20 |
| Comparative Examples 8 | D-2 | Neodymium nitrate | 0.3 | 0.21 | 0.48 | 0.29 |
| Example 1 | A-3 | Yttrium trinitrate | 0.8 | 0.21 | 0.46 | 0.78 |
| Example 2 | B-3 | Ytterbium nitrate | 0.5 | 0.21 | 0.46 | 0.48 |
| Example 3 | C-3 | Samaric nitrate | 0.2 | 0.21 | 0.47 | 0.19 |
| Example 4 | D-3 | Neodymium nitrate | 0.3 | 0.21 | 0.47 | 0.28 |
Table 2
| The catalyzer numbering | Pt, heavy % | Re, heavy % | RE, heavy % |
| A-2 | 0.20 0.23 0.21 | 0.45 0.51 0.48 | 0.76 0.79 0.76 |
| B-2 | 0.21 0.19 0.24 | 0.46 0.44 0.50 | 0.48 0.48 0.51 |
| C-2 | 0.18 0.22 0.23 | 0.45 0.48 0.52 | 0.19 0.18 0.18 |
| D-2 | 0.18 0.22 0.25 | 0.45 0.47 0.50 | 0.27 0.28 0.30 |
| A-3 | 0.21 0.22 0.21 | 0.47 0.46 0.46 | 0.77 0.77 0.77 |
| B-3 | 0.21 0.21 0.21 | 0.46 0.47 0.47 | 0.48 0.48 0.48 |
| C-3 | 0.21 0.21 0.22 | 0.47 0.48 0.47 | 0.18 0.18 0.18 |
| D-3 | 0.21 0.21 0.21 | 0.47 0.47 0.48 | 0.28 0.28 0.28 |
Table 3
| Initial boiling point/final boiling point, | Density d | 20, grams per cubic centimter | Hydrocarbon is formed, heavy % | ||
| Alkane | Naphthenic hydrocarbon | Aromatic hydrocarbons | |||
| 85/175 | 0.7274 | 54.78 | 40.68 | 4.54 | |
Table 4
| The catalyzer numbering | Temperature of reaction, ℃ | Transformation efficiency, heavy % | Liquid is received, heavy % | Virtue contains, heavy % |
| A-3 | 490 510 | 116.5 123.9 | 82.1 77.2 | 59.0 66.7 |
| A-2 | 490 510 | 108.6 118.2 | 81.6 76.7 | 55.4 64.1 |
| B-3 | 490 510 | 135.4 143.0 | 82.3 76.8 | 68.4 77.4 |
| B-2 | 490 510 | 133.4 140.6 | 81.1 76.3 | 68.4 76.6 |
Claims (10)
1, a kind of preparation method of multimetal reforming catalyst, described catalyzer comprises the platinum of 0.1～2.0 heavy %, 0.1 the rhenium of～2.0 heavy %, 0.2 the chlorine of～3.0 heavy %, 0.01～2.0 heavy % lanthanide series metal or yttrium and inorganic high-temperature resistant oxide carriers, it is characterized in that this Preparation of catalysts comprises platiniferous, rhenium, lanthanide series metal or yttrium, the water-soluble cpds of chlorine is mixed with steeping fluid, the amount of steeping fluid is 1.1～5.0 times of carrier saturated adsorption capacity, impregnated carrier under 0.001～0.08MPa and rotating conditions, roasting then, described dipping temperature is 20～80 ℃, time is 1～8 hour, and rotational line speed is 0.01～1.0 meter per second.
2, in accordance with the method for claim 1, it is characterized in that described lanthanide series metal is selected from ytterbium, samarium or neodymium, its content is 0.1～1.0 heavy %.
3, in accordance with the method for claim 1, it is characterized in that described carrier is an aluminum oxide.
4, according to described any one method of claim 1～3, the pressure when it is characterized in that flooding is 0.005～0.05MPa, and maturing temperature is 400～700 ℃.
5, in accordance with the method for claim 4, it is characterized in that dipping temperature is 40～60 ℃, rotational line speed is 0.05～0.5 meter per second, and the steeping fluid consumption is 1.1～3.0 times of carrier saturated adsorption capacity.
6, according to described any one method of claim 1～3, it is characterized in that containing platinic compound and be selected from Platinic chloride.
7, according to described any one method of claim 1～3, it is characterized in that containing rhenium compound and be selected from perrhenic acid.
8, according to described any one method of claim 1～3, the compound that it is characterized in that containing lanthanide series metal is selected from the nitrate or the muriate of lanthanide series metal.
9, in accordance with the method for claim 8, it is characterized in that the nitrate of described lanthanide series metal or nitrate or the muriate that muriate is selected from ytterbium, samarium or neodymium.
10, according to described any one method of claim 1～3, it is dry under 0.01～0.08MPa, 80～160 ℃ of conditions to it is characterized in that flooding the back carrier, then in 400～700 ℃ of roastings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02121588XA CN1181164C (en) | 2002-06-27 | 2002-06-27 | Method for preparing polymetallic reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02121588XA CN1181164C (en) | 2002-06-27 | 2002-06-27 | Method for preparing polymetallic reforming catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1465665A CN1465665A (en) | 2004-01-07 |
| CN1181164C true CN1181164C (en) | 2004-12-22 |
Family
ID=34142209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02121588XA Expired - Lifetime CN1181164C (en) | 2002-06-27 | 2002-06-27 | Method for preparing polymetallic reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1181164C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247872A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Loaded platinum catalyst and preparation method thereof |
| CN102294238B (en) * | 2010-06-22 | 2013-05-29 | 南通扬子催化剂有限公司 | Industrial soaking process for noble metal catalyst |
| CN102895995B (en) * | 2011-07-28 | 2015-07-01 | 中国石油化工股份有限公司 | Naphtha reforming catalyst and preparation method thereof |
| CN103285859B (en) * | 2012-02-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of sulphided state multimetal reforming catalyst and preparation method thereof |
| CN104841462B (en) * | 2014-02-18 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of more metal semi regeneration reforming catalysts and preparation method thereof |
| CN104841424B (en) * | 2014-02-18 | 2017-04-26 | 中国石油化工股份有限公司 | Polymetallic reforming catalyst and preparation method thereof |
| CN105717151B (en) * | 2014-12-03 | 2018-11-16 | 中国石油天然气股份有限公司 | The measuring method of platinum, samarium element in reforming catalyst |
| CN109304169B (en) * | 2017-07-27 | 2021-07-13 | 中国石油化工股份有限公司 | Reforming catalyst and process for producing the same |
| CN110064414B (en) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | Rare earth-containing semi-regenerated reforming catalyst and preparation method thereof |
| CN110064416B (en) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | Multi-metal semi-regenerated reforming catalyst and preparation method thereof |
| CN113694943A (en) * | 2021-08-26 | 2021-11-26 | 润和催化材料(浙江)有限公司 | Semi-regenerated reforming catalyst with shell-core structure and preparation method and evaluation method thereof |
-
2002
- 2002-06-27 CN CNB02121588XA patent/CN1181164C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1465665A (en) | 2004-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1181164C (en) | Method for preparing polymetallic reforming catalyst | |
| RU2146171C1 (en) | Catalytic system for catalytic hydrodesulfurization hydrodehydrogenation, reforming, hydrogenation - dehydrogenation and isomerization of hydrocarbon raw material; method of production, activation, regeneration and use | |
| KR20010014507A (en) | A catalyst material and a process for its preparation | |
| RU2674157C1 (en) | Method for regenerating deactivated catalyst for hydro-treating | |
| CN111468106A (en) | Ceramsite catalyst for sewage treatment and preparation and application methods thereof | |
| EP4023329A1 (en) | Dearsenification adsorbent and preparation method therefor | |
| KR20220068221A (en) | Metal foam supported catalyst and method for preparing same | |
| CN1216937A (en) | Three-way catalyst for treating exhaust gases | |
| CN100338189C (en) | Method for preparing reforming catalyst in platinum, stannum series | |
| Kim et al. | Easily Scalable Shell‐Structured Copper Catalyst with High Activity and Durability for Carbon Dioxide Hydrogenation | |
| CN112354518B (en) | Preparation method of zinc-iron composite oxide loaded active carbon desulfurizing agent | |
| CN1191121C (en) | Reforming Pt-Re catalyst and its prepn | |
| CN104511292A (en) | A continuous-reforming catalyst and a preparing method thereof | |
| CN111659428A (en) | Continuous reforming catalyst and preparation method and application thereof | |
| CN110064418B (en) | Oxidation state reforming catalyst and preparation method thereof | |
| CN110064414B (en) | Rare earth-containing semi-regenerated reforming catalyst and preparation method thereof | |
| CN112108108B (en) | Copper sulfide mercury removing agent and preparation method thereof | |
| CN110064422A (en) | A kind of more metal continuous reforming catalysts and preparation method thereof | |
| CN106928004B (en) | A kind of selective hydrogenation method of C 3 fractions | |
| CN111822039B (en) | Preparation method of rare earth-containing hydrocracking catalyst | |
| CN1039917C (en) | Pt-Sn-Ti multi-metal reforming catalyst | |
| US2595943A (en) | Method of hardening bauxite with calcium sulfate | |
| JP3590654B2 (en) | Hydrocarbon steam reforming method | |
| CN1715370A (en) | Process for preparing poly metal reforming catalyst | |
| CN110064416B (en) | Multi-metal semi-regenerated reforming 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041222 |
|
| CX01 | Expiry of patent term |