CN1351123A - Process for preparing carrier of hydrocracking catalyst - Google Patents
Process for preparing carrier of hydrocracking catalyst Download PDFInfo
- Publication number
- CN1351123A CN1351123A CN 00123159 CN00123159A CN1351123A CN 1351123 A CN1351123 A CN 1351123A CN 00123159 CN00123159 CN 00123159 CN 00123159 A CN00123159 A CN 00123159A CN 1351123 A CN1351123 A CN 1351123A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- acid solution
- accordance
- acid
- catalyst
- 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
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A process for preparing the carrier of hydrocracking catalyst features that the molecular sieve to be used is processed by medium or strong acid, especially the nitric acid with strong oxidizing power to increase distance of acid centers, decrease the number of acid center, and change the intensity of acid centers, and the secondary pores are added for lowering secondary cracking. Its catalyst features high activity stability and selectivity in high-nitrogen condition.
Description
The present invention relates to a kind of preparation method of carrier of hydrocracking catalyst, especially for the preparation method of preparation medium oil type hydrocracking catalyst carrier.
Hydrocracking process is one of important means of heavy oil lighting in the petroleum refining process, hydrocracking catalyst is the core of this technology, the dual-function catalyst that hydrocracking catalyst is made up of hydrogenation metal component and acidic components, this catalyzer not only has hydrogenation activity, and has cracking and heterogeneous activity.The hydrogenation metal component of hydrocracking catalyst mainly is the metallic element (Ni, Mo, W, Co, Pd, Pt etc.) of VI-B family and VIII family, or is their oxide compound or sulfide.Typical acidic components comprise unformed SiO
2-Al
2O
3Contain F or P aluminum oxide and zeolite molecular sieve series, in addition, also need add a part of aluminum oxide, the effect of playing dispersed metal, reducing second pyrolysis, improve intensity and improve middle distillates oil selectivity.Industrial technical process commonly used has one section, two sections and the three kinds of technical process of connecting.
Best hydrocracking catalyst must be that hydrogenation activity and cracking activity are complementary, and generally according to the raw material oil properties, production purpose product and technological process prepare corresponding catalyzer.Because the demand of intermediate oil increases day by day, therefore require hydrocracking catalyst volume increase intermediate oil, want hydrogenation activity strong for the catalyzer of volume increase intermediate oil, acid moderate, the acid sites number is not too many, in order to avoid cause too much second pyrolysis.
The acidic components of unformed hydrocracking catalyst are unformed SiO
2-Al
2O
3Contain F, B or P aluminum oxide, because a little less than its acidity, the acid sites number is few, therefore, the middle distillates oil selectivity of unformed hydrocracking catalyst is good, still, unformed hydrocracking catalyst active low, insensitive to temperature variation, flexibility of operation is poor.
Molecular sieve acid site number is many, and acid site intensity height is widely used as the acidic components of hydrocracking catalyst.The molecular sieve that is used to do hydrocracking catalyst mainly is a Y zeolite, also has beta molecular sieve and ZSM-5 series molecular sieve.Traditional Y zeolite acid site number is too much, and the heavy hydrocarbon molecule enters and arrives acid sites in the pore structure of molecular sieve and suffer a cracking, and reactant is adsorbed on contiguous acid sites again and suffers second pyrolysis, causes the catalyzer middle distillates oil selectivity poor.For acidity and the catalyzer middle distillates oil selectivity that makes molecular sieve reaches suitable balance, need carry out modification to molecular sieve.The modified method of molecular sieve mainly contains two kinds of ion-exchange and dealuminzations.The aluminium content height of Y zeolite, a little less than the acidity, the acid site number is many, the Y zeolite dealuminzation can improve the silica alumina ratio of molecular sieve, improves strength of acid, reduces the acid site number, and can form secondary pore, reduce second pyrolysis effectively, so the dealuminzation of Y zeolite is one of molecular sieve modified most important means, following patent has been described the method for modifying of molecular sieve:
US.Pat. № 5,464, and 527 have described a kind of preparation method of rare earth UHPY molecular sieve, and preparation process is: a) ammonium partly exchanges silica alumina ratio less than 6.0 NaY molecular sieve; B) molecular sieve that obtains of hydrothermal treatment consists a step; C) secondary ammonium exchange; D) molecular sieve that obtains of hydrothermal treatment consists c step, the lattice constant that makes it is less than 24.35 dusts; E) molecular sieve that obtains of rare earth exchanged d step.
English Patent GB-A-2114,594 have described a kind of preparation method who is used for intermediate oil hydrocracking catalyst reaming faujasite molecular sieve, and preparation process is as follows: a) steam treatment faujasite molecular sieve, temperature are preferably in more than 760 ℃ greater than 538 ℃; B) faujasite molecular sieve crossed of acid treatment steam treatment, preferably pH is less than 2.
Should be noted that English Patent GB-A-2 is in the preparation process of 114, the 594 reaming faujasite molecular sieves of describing, along with the SiO of the increase molecular sieve of acid solutions
2/ Al
2O
3Mol ratio has certain raising, and degree of crystallinity decreases, the main purpose of the acid solution treatment step in the patent is a dealuminzation, next is to remove the unformed aluminum oxide of taking off in the steam treatment step, rather than the degree of crystallinity of reduction molecular sieve, the crystalline structure of saboteur sieve is so the used acid solution amount of every mol sieve is less and acid solutions is lower in the preparation process of the reaming faujasite molecular sieve that embodiment describes in the patent.
In addition, English Patent GB-A-2, the used acid of acid treatment process is hydrochloric acid in 114,594, has the strong acid of strong oxidizing property such as nitric acid the crystalline structure of molecular sieve is had very strong destruction, therefore, English Patent GB-A-2, the acid treatment process is unsuitable for the strong acid with strong oxidizing property in 114,594, perhaps require its concentration lower when with the strong acid of strong oxidizing property, consumption is less.
The method of modifying of the described molecular sieve of above-mentioned patent, the method of modifying complexity, technological line is long, every controlling index strictness, resulting molecular sieve crystallinity height, the strength of acid in acid site is big, easily and the effect of alkali nitrogen and inactivation, the molecular sieve crystallinity height also is unfavorable for strong acid center uniform distribution in support of the catalyst of molecular sieve, therefore, influences the intermediate oil selectivity of hydrocracking catalyst.Modified Zeolite Y alkali resistant nitrogen ability, when they were used as the acidic components of hydrocracking catalyst, stock oil must carry out pre-treatment.
The object of the present invention is to provide a kind of acidity suitable, the preparation method of the carrier of hydrocracking catalyst that middle distillates oil selectivity is high.
The preparation method of carrier of hydrocracking catalyst of the present invention is: molecular sieve is mixed with aluminum oxide and/or oxidation sial, and moulding makes support of the catalyst then, and molecular sieve wherein is the molecular sieve after handling with acid solution.
The concrete preparation method of carrier of hydrocracking catalyst of the present invention is, molecular sieve join in the acid solution stir for some time after, molecular sieve can separate with acid solution, drying, is mixed with carrier of hydrocracking catalyst with aluminum oxide and/or oxidation sial again; Molecular sieve can not separate with acid solution yet, and the mixed solution of molecular sieve and acid solution adds entry, little porous aluminum oxide is made tackiness agent, is mixed and made into the plasticity-mashed prod with aluminum oxide or oxidation sial then, makes carrier of hydrocracking catalyst through moulding process.
Suitable molecular sieve comprises Y zeolite and Modified Zeolite Y; β type and modification beta molecular sieve; ZSM-5 series molecular sieve.Suitable acid comprises inorganic or organic middle strong acid, for example, and nitric acid, hydrochloric acid, phosphoric acid etc.Suitable acid solution pH＜2.The suitable treatment time is 5～120 minutes.
As follows by molecular sieve acid treatment actual conditions of the present invention:
(1) preparating acid solution, suitable acid are inorganic or organic middle strong acid; Suitable acid solutions is 0.01M～10M, and suitable acid solutions is 0.05M～8M, and optimum acid solutions is 0.1M～6M.As use hydrochloric acid a little less than the oxidisability, phosphoric acid etc., its concentration can be suitably high, can be 1M～10M as concentration; If use the strong nitric acid of oxidisability, because of its destructive force is strong, concentration can be hanged down, and can be 0.01M～6M as concentration.
(2) acid solution that configures is joined in the container that fills a certain amount of molecular sieve, and stir.Suitable acid solution consumption is 2ml～12ml/g molecular sieve, and suitable acid solution consumption is 4ml～10ml/g molecular sieve, and optimum acid solution consumption is 5ml～9ml/g molecular sieve.Suitable churning time is 5～120 minutes, and suitable churning time is 10～90 minutes, and optimum churning time is 20～60 minutes.
(3) after acid solution was handled molecular sieve, molecular sieve can wash with acid solution, filters, dry, pulverize, be mixed with carrier of hydrocracking catalyst with aluminum oxide and/or oxidation sial; Molecular sieve can not separate with acid solution yet, with the mixed solution of molecular sieve and acid solution add entry, little porous aluminum oxide is made tackiness agent, be mixed and made into the plasticity-mashed prod with aluminum oxide and/or oxidation sial then, make carrier of hydrocracking catalyst through moulding process.
The used acid solution of the present invention most preferably is salpeter solution, and used molecular sieve most preferably is super-stable Y molecular sieves.
The method of modifying of molecular sieve mainly is appropriate dealuminzation, regulates acid site quantity, intensity and the acid site type of molecular sieve.Key problem in technology of the present invention is with strong acid solution molecular sieve to be handled, particularly the strong acid solution of high density is handled, it is strong most preferably to be oxidisability, the salpeter solution that destructive force is strong is handled, the suitably excessive dealuminzation of molecular sieve after the processing, the crystalline structure of part erosion damage molecular sieve equably, make the unordered short range order of crystalline structure long-range of molecular sieve, the acid site of molecular sieve is apart from increase, reduce the acid site quantity of molecular sieve, improve acid site intensity, regulate the acid site type of molecular sieve, zeolite crystal diminishes, and increases the dispersity of acid site in catalyzer of molecular sieve, simultaneously excessive dealuminzation corrodes and has increased secondary pore, reduce second pyrolysis, simultaneously, excessively dealuminzation has also increased the silicon hydroxyl.These have all increased the selectivity of molecular sieve to middle distillate.
Another advantage of the present invention is, after acid solution is handled molecular sieve, molecular sieve can not separate with acid solution, the mixed solution of molecular sieve and acid solution adds entry, little porous aluminum oxide is made tackiness agent, be mixed and made into the plasticity-mashed prod with aluminum oxide or oxidation sial then, make carrier of hydrocracking catalyst through moulding process.Thereby shortened flow process greatly, and reduced treatment step, reduced cost and enhanced productivity.
The feature that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Example one
Step 1 preparation 1M salpeter solution;
Step 2 is got the acid solution 140ml that step 1 configures and is joined in the container that fills 30g super-stable Y molecular sieves (degree of crystallinity 89, lattice constant 2.445nm, silica alumina ratio 10.2), and stirs 30 minutes.
Step 3 with the resulting molecular sieve of step 2 separate with acid solution, wash, filter, dry, pulverize and make modified molecular screen.
Example two
Step 1 is with example one step 1;
Step 2 is with example one step 2;
Step 3 is made tackiness agent with the mixed solution adding 100ml water and the 50gSB aluminum oxide of resulting molecular sieve of step 2 and acid solution.
Example three
Step 1 preparating acid 4N hydrochloric acid soln;
Step 2 joins the acid solution 150ml that configures in the container that fills 30g super-stable Y molecular sieves (degree of crystallinity 89, lattice constant 2.445nm, silica alumina ratio 10.2), and stirs 30 minutes;
Step 3 with the resulting molecular sieve of step 2 separate with acid solution, wash, filter, dry, pulverize and make modified molecular screen;
Comparative example one
By English Patent GB-A-2, the preparation method of the used molecular sieve of B catalyzer produces in the example three in 114,594.
Example four
The preparation catalyzer
Get a kind of macropore silicon oxide aluminium 240g (silica alumina ratio 0.4, pore volume 310ml/g, specific surface 0.65m
2/ g, mean pore size 8.5nm), SB aluminum oxide 70g mixes and add suitable quantity of water with molecular sieve that example one, example three, comparative example one obtain respectively and the nitric acid extruded moulding is made carrier, then respectively with W-Ni steeping fluid dipping, obtains catalyst A, catalyzer C and catalyzer D after roasting.
Example five
The preparation catalyzer
Get a kind of macropore silicon oxide aluminium 240g (silica alumina ratio 0.4, pore volume 310ml/g, specific surface 0.65m
2/ g, mean pore size 8.5nm), SB aluminum oxide 70g mixes with the bonding agent that example two obtains, and extruded moulding is made carrier, with W-Ni steeping fluid dipping, obtains catalyst B after roasting.
Comparative example two
Prepare the super-stable Y molecular sieves catalyzer that is untreated
Get a kind of super-stable Y molecular sieves 30g (degree of crystallinity 89, lattice constant 2.445nm, silica alumina ratio 10.2), a kind of macropore silicon oxide aluminium 240g (silica alumina ratio 0.4, pore volume 310ml/g, specific surface 0.65m
2/ g, mean pore size 8.5nm), SB aluminum oxide 70g mixes the adding suitable quantity of water and the nitric acid extruded moulding is made carrier, then respectively with W-NI steeping fluid dipping, obtains catalyzer E after roasting.
Comparative example three
The preparation amorphous catalyst
Get a kind of macropore silicon oxide aluminium 240g (silica alumina ratio 0.4, pore volume 310ml/g, specific surface 0.65m
2/ g, mean pore size 8.5nm), SB aluminum oxide 100g makes carrier with adding suitable quantity of water and nitric acid extruded moulding, with W-Ni steeping fluid dipping, obtains catalyzer F after roasting.
Example six
This example is catalyst activity evaluation test of the present invention, and compares with other catalyzer.Evaluation is carried out on the 200ml small hydrogenation device.Catalyst property sees Table-1, and raw materials used oil nature sees Table-2.Evaluation result see Table-3 and the table-4.Wherein table-3 is an anti-catalyst for refining that is equipped with, the nitrogen content＜10 μ g/g in the control treated oil.Table-4 is not refining section, and raw material directly carries out hydrocracking.Other processing condition are hydrogen pressure 14.7MPa, hydrogen to oil volume ratio 1240: 1, cracking catalyst gymnastics air speed 0.92h
-1
Table-1 catalyst property
| The catalyzer numbering | ????A | ????B | ????C | ????D | ????E | ?F |
| Molecular sieve preparation method and characteristics | The present invention | The present invention | The present invention | Press GB-A-2,114,594 | Add untreated ultra-steady Y molecular sieve | Unformed |
| Chemical constitution, % | ||||||
| WO 3 | ??24.11 | ??23.88 | ??23.67 | 24.08 | 23.94 | 24.17 |
| NiO | ??7.08 | ??7.22 | ??7.35 | 7.17 | 7.18 | 7.24 |
| Pore volume, ml/g | ??0.341 | ??0.349 | ??0.336 | 0.287 | 0.268 | 0.304 |
| Specific surface, m 2/g | ??191.2 | ??197.5 | ??189.4 | 217.5 | 234.0 | 174.1 |
Table-2 stock oil character
| Stock oil | ??????I |
| Density, (20 ℃) | ????0.9021 |
| Boiling range, ℃ (ASTM-D1160) | |
| IBP/10％ | ????281/349 |
| 30％/50％ | ????397/432 |
| 70％/90％ | ????460/501 |
| 95％/EP | ????520/538 |
| Condensation point, ℃ | ????33 |
| Carbon residue, % | ????0.07 |
| S，％ | ????1.55 |
| N，μg/g | ????1388 |
| C，％ | ????85.55 |
| H，％ | ????12.07 |
| Refractive power η D20 | ????1.4875 |
Table-3 catalyst activity evaluation results ()
| Catalyzer | ??A | ??B | ??C | ??D | ??E | ??F |
| Stock oil | ????????????????????????????I | |||||
| Processing condition | ||||||
| The cracking reaction temperature, ℃ | ??375 | ??375 | ??375 | ??373 | ??368 | ??391 |
| The treated oil nitrogen content, μ g/g | ??＜10 | ??＜10 | ??＜10 | ??＜10 | ??＜10 | ??＜10 |
| ＜370 ℃ of transformation efficiencys, % | ??69.3 | ??70.1 | ??68.5 | ??67.1 | ??72.0 | ??65.3 |
| 132～370 ℃/＜370 ℃ middle distillates oil selectivities, % | ??83.1 | ??83.9 | ??82.4 | ??76.0 | ??58.3 | ??84.1 |
Table-4 catalyst activity evaluation results (two)
| Catalyzer | ??A | ??B | ??C | ??D | ??E | ??F |
| Stock oil | ?????????????????????????I | |||||
| Processing condition | ||||||
| The cracking reaction temperature, ℃ | 405 | ?405 | ?405 | ?413 | ?415 | ?413 |
| ＜370 ℃ of transformation efficiencys, % | 67.3 | ?69.5 | ?65.7 | ?59.8 | ?39.3 | ?55.5 |
| 132～370 ℃/＜370 ℃ middle distillates oil selectivities, % | 81.9 | ?83.3 | ?81.6 | ?74.7 | ?46.3 | ?83.7 |
The method for preparing catalyst difference, they are active different with selectivity.By table 3 as seen, under the condition of control treated oil nitrogen content＜10 μ g/g, adopt activity of such catalysts of the present invention to be lower than reference catalyst D and E, but selectivity is better than each reference catalyst.By table-4 as seen, instead not adorning catalyst for refining one is under the high nitrogen condition, adopts activity of such catalysts of the present invention and selectivity all obviously to be better than each reference catalyst.By above example as can be seen, catalyzer of the present invention not only has higher activity, and middle distillates oil selectivity is preferably arranged.
Compared with prior art, preparation process of the present invention is simple, excessively acid treatment, the crystal structure of part erosion damage molecular sieve equably, make the unordered shortrange order of crystal structure long-range of molecular sieve, the acid site of molecular sieve is apart from increase, reduce the acid site quantity of molecular sieve, improve acid site intensity, the acid site type of Molecular regulator sieve, zeolite crystal diminishes, make the acid site of molecular sieve in catalyst, be easy to disperse, excessively the dealuminzation erosion has increased secondary pore simultaneously, reduces second pyrolysis, therefore, adopt the catalyst of the hydrocracking carrier of the present invention's preparation to have higher middle distillates oil selectivity and activity, and instead not filling catalyst for refining one is under the high nitrogen condition, and activity and selectivity all obviously is better than each reference catalyst.
Claims (16)
1, a kind of preparation method of carrier of hydrocracking catalyst mixes molecular sieve with aluminum oxide and/or oxidation sial, moulding makes support of the catalyst then, it is characterized in that the molecular sieve of used molecular sieve for handling through acid solution.
2, in accordance with the method for claim 1, it is characterized in that the condition that described molecular sieve is handled with acid solution is:
(1) preparating acid solution, the concentration of acid solution are 0.01M～10M;
(2) molecular sieve is joined in the container that fills the acid solution for preparing, stirred 5-120 minute.
3, in accordance with the method for claim 2, it is characterized in that the molecular sieve after described acid solution is handled washs, filter, dry, pulverize and make modified molecular screen, be used to prepare support of the catalyst then.
4, in accordance with the method for claim 2, the mixed solution that it is characterized in that molecular sieve after described acid solution is handled and acid solution directly adds entry, little porous aluminum oxide is made tackiness agent, is used to prepare support of the catalyst then.
5, in accordance with the method for claim 2, it is characterized in that described molecular screening is from Y zeolite, Modified Zeolite Y, beta-molecular sieve, modification beta molecular sieve or ZSM-5 series molecular sieve.
6, in accordance with the method for claim 2, it is characterized in that described acid comprises inorganic or organic middle strong acid.
7, in accordance with the method for claim 2, it is characterized in that described acid solution is salpeter solution, phosphoric acid solution or hydrochloric acid soln.
8, in accordance with the method for claim 2, the concentration that it is characterized in that described acid solution is 0.05M～8M.
9, in accordance with the method for claim 2, it is characterized in that described acid solutions is 0.1M～6M.
10, in accordance with the method for claim 2, it is characterized in that described acid solution consumption is 2ml～12ml/g molecular sieve.
11, in accordance with the method for claim 2, it is characterized in that described acid solution consumption is 4m～10ml/g molecular sieve.
12, in accordance with the method for claim 2, it is characterized in that described acid solution consumption is 5ml～9ml/g molecular sieve.
13, in accordance with the method for claim 2, it is characterized in that described churning time is 10～90 minutes.
14, in accordance with the method for claim 2, it is characterized in that described churning time is 20～60 minutes.
15, in accordance with the method for claim 2, it is characterized in that described acid solution is a salpeter solution.
16, in accordance with the method for claim 2, it is characterized in that used molecular sieve is a super-stable Y molecular sieves.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123159 CN1107711C (en) | 2000-10-26 | 2000-10-26 | Process for preparing carrier of hydrocracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123159 CN1107711C (en) | 2000-10-26 | 2000-10-26 | Process for preparing carrier of hydrocracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351123A true CN1351123A (en) | 2002-05-29 |
| CN1107711C CN1107711C (en) | 2003-05-07 |
Family
ID=4589634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00123159 Expired - Lifetime CN1107711C (en) | 2000-10-26 | 2000-10-26 | Process for preparing carrier of hydrocracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1107711C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331604C (en) * | 2004-06-21 | 2007-08-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN102451773A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst |
| CN104549427A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | High-quality chemical raw material hydrocracking catalyst and preparation method thereof |
-
2000
- 2000-10-26 CN CN 00123159 patent/CN1107711C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331604C (en) * | 2004-06-21 | 2007-08-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN102451773A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst |
| CN102451773B (en) * | 2010-10-15 | 2013-10-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst |
| CN104549427A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | High-quality chemical raw material hydrocracking catalyst and preparation method thereof |
| CN104549427B (en) * | 2013-10-23 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of high-quality industrial chemicals hydrocracking catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1107711C (en) | 2003-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1854258A (en) | Cracking catalyst | |
| CN1253859A (en) | Hydrocracking catalyst for producing middle distillate and its preparation method | |
| CN100513531C (en) | Hydrocracking method of midbarrel oil circulation | |
| CN1054153C (en) | Hydrocracking catalyst for producing intermediate fraction oil | |
| CN1778873A (en) | Inferior diesel hydrogenation catalyst | |
| CN1778872A (en) | Hydrogenation desulfurized catalyst containing molecular screen | |
| CN1955260A (en) | Hydrocracking method | |
| CN1043520A (en) | A kind of catalyst for cracking of producing low-carbon alkene | |
| CN107345161A (en) | A kind of method for hydrogen cracking of coal tar | |
| CN1107711C (en) | Process for preparing carrier of hydrocracking catalyst | |
| CN1209442C (en) | Catalytic cracking catalyst and its prepn | |
| CN101328430B (en) | Method for hydro-dearomatization for catalyzing diesel | |
| CN1253860A (en) | Gamma-zeolite contained middle distillate type hydrocracking catalyst and its preparation | |
| CN1144861C (en) | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. | |
| CN1147574C (en) | Hydrocracking catalyst for inceasing output of jet fuel and diesel oil | |
| CN1955263A (en) | Combined processing method of faulty catalytic cracking diesel oil | |
| CN1132898C (en) | Petroleum catalytic cracking catalyst | |
| CN1766052A (en) | Distillate oil hydrogenation catalyst and its preparation method | |
| CN1955259A (en) | Parallel hydrocracking method | |
| CN1048428C (en) | Multi-zeolite catalyzer for preparation of low-carbon olefines | |
| CN1205317C (en) | Nobel metal hydrogen cracking catalyst and its preparing method | |
| CN1218784C (en) | Medium oil type hydrocracking catalyst | |
| CN1031409C (en) | Assistant for increasing octane value of gasoline and yield rate of propene and butene | |
| CN1147573C (en) | Noble metal catalyst for hydrogenation and its prepn | |
| CN1955258A (en) | Hydrocracking method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030507 |
|
| CX01 | Expiry of patent term |