CN1043520A - A kind of catalyst for cracking of producing low-carbon alkene - Google Patents
A kind of catalyst for cracking of producing low-carbon alkene Download PDFInfo
- Publication number
- CN1043520A CN1043520A CN 88108669 CN88108669A CN1043520A CN 1043520 A CN1043520 A CN 1043520A CN 88108669 CN88108669 CN 88108669 CN 88108669 A CN88108669 A CN 88108669A CN 1043520 A CN1043520 A CN 1043520A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- zsm
- heavy
- zeolite
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of catalyst for cracking, its carrier are the clay of the heavy % of 0-70 and the inorganic oxide of the heavy % of 5-99, and its active ingredient is the ZSM-5 of the heavy % of 1-50 and the mixture of Y zeolite.The ZSM-5 molecular sieve accounts for the heavy % of 75-100 in the active ingredient, and Y zeolite accounts for the heavy % of 0-25.This catalyst for cracking is applicable to the production low-carbon alkene, especially propylene and butylene.This catalyzer is applicable to the stock oil of the various boiling range scopes that comprise mink cell focus.
Description
The present invention relates to a kind of catalyzer that is used for the petroleum hydrocarbon catalytic pyrolysis process, in particular for produce the catalyzer of low-carbon alkene by the petroleum hydrocarbon catalytic pyrolysis process.
Low-carbon alkene is the petrochemical materials of having many uses, produce low-carbon alkene from petroleum hydrocarbon, generally adopting with Sweet natural gas, petroleum naphtha or solar oil is the thermo-cracking of raw material and the methods such as heat carrier cracking of heavy hydrocarbon, also by-product low-carbon alkene when general catalytic cracking petroleum hydrocarbons process is produced gasoline and solar oil, and its output only accounts for below 15% of stock oil.
Adopt catalyst cracking method, from the existing many patent reports of hydrocarbon production low-carbon alkene, in partial monopoly, be to use metal load type catalyst, carrier can be silicon oxide, aluminum oxide or other oxide compound, and used metallic element belongs to II B, V B, VII B and VIII B family element more, and they all have hydrogenation, dehydrogenation activity, under the cracking reaction condition of high temperature and low pressure, show dehydrogenation activity, accelerate generation (USP3,541,179 of low-carbon alkene thus; USP3,647,682; DD225-135, SU1,214,726).USP3 for example, the catalyzer of using in 541,179 is an active ingredient with elements such as copper, manganese, chromium, vanadium, zinc, silver or cadmiums, is carrier with aluminum oxide or silicon oxide.When using this type of catalyzer,, carrying out cracking reaction simultaneously because metallic element has dehydrogenation, main pay relevant with dehydrogenation reacted, i.e. polymerization coking reaction, also corresponding quickening, make on the catalyzer knot charcoal more, thereby can only adopt lightweight material (full boiling point is generally less than 220 ℃).
Be to use solid acid catalyst in the partial monopoly in addition, DD152 has introduced in 356 and has used amorphous aluminum silicide to be catalyzer, and the catalytic cracking reaction that carries out gasoline and vacuum gas oil under 600～800 ℃ is to produce low-carbon alkene, C
2～C
4The about 30%(of olefins yield for example, ethene 13.5%, propylene 6.3%, butylene 10.5%).JP60-224, having introduced with the ZSM-5 molecular sieve in 428 is active ingredient, aluminum oxide is the catalyzer of carrier, under 600～750 ℃ of temperature of reaction, catalytic cracking C
5～C
25The paraffinic hydrocarbon raw material, C
2～C
4Olefins yield is about 30% (for example: air speed 20～300 hours
-1, petroleum naphtha is a raw material, ethene 16%, propylene 14.1%; Butylene 1.8%).When adopting above technology, the temperature of reaction height requires highly to equipment material, and the boiling spread of reaction raw materials is narrow, and stock oil is lighter, and ethene is more in the product.
In recent years, in order to improve the octane value of the gasoline that catalytic cracking process produces, people add in catalytic cracking unit or catalyzer and select shape additive (USP4,309,280, USP4 on a small quantity, 521,298, USP4,552,648, USP3,894,933, USP4,522,705).USP4 has reported in 309,280 and will account for catalyzer and weigh 0.01～1% HZSM-5 and add in the reaction unit separately.USP3,758, having described with type ZSM 5 molecular sieve and large pore molecular sieve (as X, Y type) (both ratios can be 1: 10～3: 1) in 403 is active ingredient, the catalyzer that carrier can have (carrier is that inorganic oxide, carrier account for catalyzer and weigh 99～5%) not have, adopt this catalyzer, when improving gasoline octane rating, also increased C
3, C
4The yield of alkene, but amount is seldom, and for example, the dry gas yield is about 8 heavy %, C
3～C
4Olefin yields is about 10 heavy %.
The purpose of this invention is to provide and a kind ofly be used to produce low-carbon alkene, especially propylene and butylene, and the catalyst for cracking of double steam oil and diesel oil.
The carrier of catalyzer provided by the invention is that 0～70%(is in catalyst weight) clay and 5～99% inorganic oxide, active ingredient is the mixture of 1～50%ZSM-5 and Y zeolite; ZSM-5 accounts for 75～100 heavy % in the active ingredient, and Y zeolite accounts for 0～25 heavy %.
The ZSM-5 molecular sieve is SiO preferably
2/ Al
2O
3Than the HZSM-5 molecular sieve that is 20～200; Y zeolite can be the Y zeolite that has exchanged through rare earth ion or handled through physics and/or chemical process, preferably the Y zeolite after physics and/or chemical process are carried out stabilization treatment; Inorganic oxide can be silicon oxide, aluminum oxide or amorphous aluminum silicide; Clay can be various clays natural or synthetic, that be generally used for cracking catalyst carrier, as kaolin, halloysite etc.
Preparation of catalysts method provided by the invention can have following two kinds:
The method I:
(1) make aluminium colloidal sol, silicon sol or silicon-aluminum sol or gel according to a conventional method, colloidal solution can be tart, and preferably PH is 2～4, and adding accounts for catalyzer and weighs 0～70% clay, stirs, and is warming up to 50～100 ℃, left standstill aging 0.5～2 hour,
(2) after the mixture of the ZSM-5 molecular sieve of predetermined amount or ZSM-5 and Y zeolite adds the water making beating, add in (1) the step gains, mix, moulding according to a conventional method, washing, filtration, drying get product again.
The method II:
(1) clay adds the water making beating, add a kind of in the mineral acid comprise hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid etc., make slurries be acid, PH2～4 preferably, add a kind of inorganic oxide that comprises aluminum oxide and precursor, silicon oxide and precursor thereof and silica-alumina and precursor thereof then, stir, be warming up to 50～100 ℃, left standstill aging 0.5～2 hour.
(2) after the mixture of the ZSM-5 molecular sieve of predetermined amount or ZSM-5 and Y zeolite adds the water making beating, add in (1) the step gains, mix, moulding according to a conventional method, washing, filtration, drying get product again.
Said ZSM-5 molecular sieve can prepare the method for ZSM-5 with routine among the present invention, and for example hydrothermal synthesis method makes.For example, be raw material with a certain amount of water glass, Tai-Ace S 150, water and template, under 100～170 ℃, under agitation react certain hour, promptly get sodium type ZSM-5 molecular sieve; Through the ion exchange process of routine, get final product the ammonium type; The latter can be converted into Hydrogen through roasting.Used template can be various organic amino, inorganic ammonia or the non-ammonia type compounds that are commonly used for template.
The catalyzer of making can carry out the processing of processes such as ion-exchange and/or roasting.
The catalytic cracking reaction that adopts catalyzer provided by the invention to carry out petroleum hydrocarbon has following advantage to produce low-carbon alkene:
(1) temperature of reaction is 500～650 ℃, and best 550～620 ℃ is low than the temperature of reaction (600～800 ℃) of prior art.
(2) C
2～C
4The alkene overall yield weighs % up to 40 of raw material, (prior art is 15～30 heavy %).
(3) C
2～C
4Account for the overwhelming majority (C for example with propylene and butylene in the alkene
2=6.1%, C
3=21.0%, C
4=14.3%), and prior art be mostly the ethene amount the highest relatively (as JP60-222, in 428, C
2=16%, C
3=14.1%, C
4=1.8%).
When (4) adopting catalyzer of the present invention, the octane value of gained gasoline is than the octane value height of conventional catalytically cracked gasoline, and the BTEX aromaticity content is also high in the gasoline.
Below will the invention will be further described by example.
Example 1
300 distilled water that restrain and 100 are restrained kaolin, and (the Suzhou machine selects 2
#) (in butt) mix, and adds concentration and be 10 milliliters of hydrochloric acid (Beijing Chemical Plant) solution of 33 heavy %, adds the pseudo-boehmites (Shandong Aluminum Plant's product) (in butt) of 50 grams again, stir.These slurries were worn out 1 hour down at 60～70 ℃, were HZSM-5(Shanghai dying seven factories of 40 heavy % again with a certain amount of solid content, SiO
2/ Al
2O
3Than being 60) aqueous slurry mix, filter, washing, 250 ℃ of dryings 2 hours, abrasive flour promptly gets and contains 18 heavy %HZSM-5 molecular sieves, 54.7 heavy % kaolin and 27.3 heavy %Al
2O
3Catalyst A.
Example 2
(Qilu Petrochemical main office Zhou village catalyst plant contains SiO to 675 gram water glass
2124 grams per liters, modulus 3.3) mixes stirring 10 minutes with 452 gram water, adding 50 ml concns is the hydrochloric acid soln of 30 heavy %, stir and add 9 milliliters of hydrochloric acid solns after 10 minutes again, stir, aging 1.5 hours, transferring solution PH with hydrochloric acid soln is 3.0～3.5, adds aluminum chloride (chemical plant, Kingsoft) solution of 176 grams, 28 heavy % subsequently, mixes, ammoniacal liquor (gold small cup chemical plant, Beijing) solution that adds 74 milliliter of 16 heavy %, be mixed, add 3 gram HZSM-5 at last and stir, more after filtration, washing, 200 ℃ of dryings 2 hours, grind, promptly get the catalyst B that contains 2 heavy %HZSM-5 and 98 heavy % amorphous silicon oxide-aluminum oxide.
Example 3
The method identical with example 1 prepares catalyzer C, different is replaces the HZSM-5 slurries with the mixed serum of a certain amount of super-stable Y molecular sieves (USY) and HZSM-5, and the catalyzer C that makes contains the kaolin of the USY by HZSM-5,1.9 heavy %, 54.0 heavy % of 17.1 heavy % and the Al of 27.0 heavy %
2O
3
Being prepared as follows of super-stable Y molecular sieves:
NaY molecular sieve (SiO
2/ Al
2O
3Than being 5.28, lattice constant is 24.65) through two friendships, two roastings, promptly with (NH
4)
2SO
4Solution exchange, roasting in the environment of air and steam, exchange and roasting once promptly get the USY molecular sieve more thereafter; Wherein give-and-take conditions are: water/NaY(is in butt) weight ratio is 15～20, (NH
4)
2SO
4/ NaY(is in butt) weight ratio is 0.5～1.0, PH3, temperature is 80～100 ℃, be 60 minutes swap time; Roasting condition is: 600～700 ℃ of temperature, 90～120 minutes time, vapour content 50%.
Example 4
The method identical with example 3 prepares catalyzer D, and just catalyzer D contains the kaolin of USY, 53.1 heavy % of HZSM-5,4.4 heavy % of 15.9 heavy % and the aluminum oxide of 26.6 heavy %.
Example 5
The method identical with example 1 prepares catalyzer E, and just catalyzer E contains the HZSM-5 molecular sieve of 48.1 heavy %, the aluminum oxide of the kaolin of 34.6 heavy % and 17.3 heavy %.
Example 6
300 gram water and 200 gram pseudo-boehmites (Shandong Aluminum Plant's product) mix, the HZSM-5(that add 50 grams are in butt) and 100 mixtures that restrain water, stir well, again after filtration, spraying drying, washing, 400 ℃ of dryings 2 hours, promptly get the catalyzer F of the aluminum oxide of the HZSM-5 that contains 200 heavy % and 80.0 heavy %.
Example 7
In small fixed flowing bed-tion reacting device, carry out the catalytic cracking reaction of vacuum gas oil (performance sees Table 1), come the performance of evaluate catalysts A, B, C, D, and and industrial cracking catalyst CRC-1(Zhou village catalyst plant product, the semi-synthetic cracking catalyst of Y-type rare earth) and ZCM-7(Zhou village catalyst plant product, the semi-synthetic cracking catalyst of superstable gamma-type) make comparisons.Catalyzer before reaction through 100% water vapor 750 ℃ of following burin-in process 4 hours.Reaction conditions: 580 ℃ of temperature, weight space velocity 1 hour
-1, agent-oil ratio 5: 1, water vapor/charge ratio 0.3, catalyzer loading amount 180 grams the results are shown in Table 2.
Transformation efficiency is that reacted gas, gasoline fraction (are C in the table 2
5～205 ℃ of cuts), coke and loss sum account for the weight percentage of raw material.Diesel oil distillate is 205～330 ℃ of cuts.
Table 1
| Density, 20 ℃, kilogram/rice 3Carbon residue, the semidine point, ℃ sulphur, heavy % nitrogen, heavy % zero pour, ℃ molecular weight, boiling range, ℃ initial boiling point 5% 10% 50% 70% 90% 95% is done | 873 0.15 ＞105 0.073 0.10 ＞50 442 346 397 411 462 489 523 535 540 |
As can be seen from the table, catalyzer provided by the invention has the approaching activity level of comparing with daily cracking catalyst, higher yield of light olefins and selectivity of light olefin preferably.
Example 8
On normal pressure pulse micro-inverse device, carry out the n-hexane cracking reaction with catalyst A, C, E or F, reaction conditions: 580 ℃ of temperature, catalyzer 0.255 gram, normal hexane is analytically pure, sample size 1 microlitre.Reaction result sees Table 3.
From table, can find out that catalyzer provided by the invention has good yield of light olefins and selectivity.
Example 9
Under the differential responses condition, in the small-sized reaction unit of the fluid catalytic cracking of cyclic regeneration, use catalyst A, carry out the cracking reaction of different material oil, the results are shown in Table 4.In addition vacuum gas oil is measured at the composition and the octane value of 580 ℃ of gasoline of producing with the reaction of paraffin vacuum gas oil down, be the results are shown in Table 5.
By table 4 as seen, under the differential responses condition, adopt the reaction of different material oil, catalyzer provided by the invention all shows good activity and selectivity of light olefin.As can be seen from Table 5, gasoline octane rating is up to 84.6, and the octane value of the gasoline of conventional catalytic cracking process production is generally about 78, and total aromatic hydrocarbons amount can reach 50.46% in the gasoline in addition, and wherein present broad-spectrum industrial chemicals-BTEX aromatic hydrocarbons (is C
8Following aromatic hydrocarbons) just have 32.36%.
Table 5
| Account for gasoline fraction, in heavy % stable hydrocarbon 10.64 alkene 38.90 aromatic hydrocarbons 50.46 bases, 2.16 in benzene 3.37 toluene 12.14 ethylbenzene, 3.69 of p-Xylol 11.00 o-Xylols, p-methyl-ethylbenzene 3.39 1,3,5 one trimethylbenzenes, 1.58 o-methylethylbenzenes 0.77 1,3,4 one trimethylbenzenes, 5.57 other aromatic hydrocarbons 6.79 |
| Motor-method octane number 84.6 |
Example 10
Prescription, flow process and processing condition by example 1 are prepared catalyzer G on full scale plant, its physical and chemical performance sees Table 6, with this catalyzer in medium-sized fluid catalytic cracking reaction unit, carry out the reaction of vacuum gas oil, and make comparisons with the reaction result of commercial catalysts ZCM-7 in medium-sized fcc riser reactor, the results are shown in Table 7.Reaction conditions during with catalyzer G is: 580 ℃ of temperature of reaction, reaction pressure (absolute pressure) 1.7 * 10
5Handkerchief, agent-oil ratio 9.8, weight space velocity 4.1 hours
-1Reaction conditions during with catalyzer ZCM-7: 494 ℃ of reaction pressures 2.33 * 10 of riser tube temperature out
5Handkerchief, agent-oil ratio 5.9.Catalyzer carried out burin-in process before reaction, and catalyzer G:750 ℃, 6 hours, 50% water vapor, catalyzer ZCM-7:780 ℃, 10 hours, 50% water vapor (handling the back micro-activity is 70).
Table 6
| Chemical constitution, heavy % Al 2O 3Na 2O Fe 2O 3SO 42- | 51.0 0.066 0.056 1.4 |
| Skeletal density, the grams per milliliter apparent density, the grams per milliliter pore volume, milliliter/gram specific surface, rice 2/ gram abrasion index, % igloss, heavy % | 2.4 0.8 0.22 191 2.8 12.0 |
| Size composition, heavy %＜20 μ m 20～80 40～80＞80 | 4.2 23.6 62.0 10.2 |
Can see that from table 6 and table 7 catalyzer of preparing with full scale plant provided by the invention has qualified physical and chemical performance, and want high catalytic rate, yield of light olefins and C than industrial cracking catalyst
= 3And C
= 4Olefine selective.
Claims (8)
1, a kind of catalyst for cracking, it is characterized in that its carrier is the clay of 0～70% (in catalyst weight) and 5～99% inorganic oxide, its active ingredient is 1～50% the ZSM-5 and the mixture of Y zeolite, ZSM-5 accounts for 75～100 heavy % in the active ingredient, and Y zeolite accounts for 0～25 heavy %.
2, catalyzer according to claim 1 is characterized in that preferably its SiO of said ZSM-5
2/ Al
2O
3Than the HZSM-5 molecular sieve that is 20～200.
3, catalyzer according to claim 1 is characterized in that said inorganic oxide is aluminum oxide, silicon oxide or amorphous aluminum silicide.
4, catalyzer according to claim 1, it is characterized in that said Y zeolite be through rare earth exchanged or through physics and/Y zeolite that chemical process was handled.
5, according to claim 1,2,3, one of 4 described catalyzer, it is characterized in that its preparation method is:
(1) in aluminium colloidal sol, silicon sol, silicon-aluminum sol or the gel, adding accounts for catalyzer and weighs 0～70% clay, stirs, and is warming up to 50～100 ℃, leaves standstill aging 0.5～2 hour;
(2) after the mixture of ZSM-5 molecular sieve or ZSM-5 and Y zeolite adds the water making beating, add in (1) the step gains, mix moulding, washing, drying.
6, according to claim 1,2,3, one of 4 described catalyzer, it is characterized in that its preparation method can be:
(1) clay adds the water making beating, add a kind of in the mineral acid comprise hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, make slurries be acid, add a kind of among silicon oxide or its precursor, aluminum oxide or precursor, amorphous aluminum silicide or the precursor then, stir, be warming up to 50～100 ℃, left standstill aging 0.5～2 hour;
(2) mixture of ZSM-5 molecular sieve or ZSM-5 and Y zeolite adds the deionized water making beating, is added in (1) the step gains, mixes, moulding, washing, drying.
7, catalyzer according to claim 5 is characterized in that said aluminium colloidal sol, silicon sol, silicon-aluminum sol or gel are tart, preferably PH2～4.
8, catalyzer according to claim 6, the PH that it is characterized in that the clay slurry in said (1) step preferably 2～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108669 CN1043520A (en) | 1988-12-21 | 1988-12-21 | A kind of catalyst for cracking of producing low-carbon alkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108669 CN1043520A (en) | 1988-12-21 | 1988-12-21 | A kind of catalyst for cracking of producing low-carbon alkene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1043520A true CN1043520A (en) | 1990-07-04 |
Family
ID=4835156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108669 Pending CN1043520A (en) | 1988-12-21 | 1988-12-21 | A kind of catalyst for cracking of producing low-carbon alkene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043520A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380690A (en) * | 1993-03-29 | 1995-01-10 | China Petro-Chemical Corporation | Cracking catalyst for the production of light olefins |
| WO1995012562A1 (en) * | 1993-11-05 | 1995-05-11 | China Petro-Chemical Corporation | A high productive process for production of lower olefins by catalytic conversion |
| EP0925831A2 (en) | 1997-12-23 | 1999-06-30 | China Petrochemical Corporation | Pillared clay catalyst for catalytic cracking of heavy oil, method for preparation and use thereof |
| CN1048428C (en) * | 1994-07-15 | 2000-01-19 | 中国石油化工总公司 | Multi-zeolite catalyzer for preparation of low-carbon olefines |
| CN1048427C (en) * | 1994-02-18 | 2000-01-19 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| US6416656B1 (en) | 1999-06-23 | 2002-07-09 | China Petrochemical Corporation | Catalytic cracking process for increasing simultaneously the yields of diesel oil and liquefied gas |
| CN1087652C (en) * | 1996-02-29 | 2002-07-17 | 中国科学院大连化学物理研究所 | Catalyst for reaction of alpha-olefines prepared through ether cracking |
| CN1301794C (en) * | 2004-08-06 | 2007-02-28 | 董家禄 | Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process |
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| CN100406416C (en) * | 2006-07-03 | 2008-07-30 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
| CN100464847C (en) * | 2004-03-10 | 2009-03-04 | 中国科学院大连化学物理研究所 | Composite zeolite catalyst for preparing alcohol and ether compounds and preparation thereof |
| CN101116827B (en) * | 2006-07-31 | 2010-12-01 | 中国石油化工股份有限公司 | Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking and its uses |
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| CN116239467A (en) * | 2022-12-13 | 2023-06-09 | 南通宝凯药业有限公司 | Preparation method of high-purity difluoroethyl acetate |
-
1988
- 1988-12-21 CN CN 88108669 patent/CN1043520A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380690A (en) * | 1993-03-29 | 1995-01-10 | China Petro-Chemical Corporation | Cracking catalyst for the production of light olefins |
| WO1995012562A1 (en) * | 1993-11-05 | 1995-05-11 | China Petro-Chemical Corporation | A high productive process for production of lower olefins by catalytic conversion |
| US5670037A (en) * | 1993-11-05 | 1997-09-23 | China Petro-Chemical Corporation | Process for producing light olefins by catalytic conversion of hydrocarbons |
| CN1048427C (en) * | 1994-02-18 | 2000-01-19 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| CN1048428C (en) * | 1994-07-15 | 2000-01-19 | 中国石油化工总公司 | Multi-zeolite catalyzer for preparation of low-carbon olefines |
| CN1087652C (en) * | 1996-02-29 | 2002-07-17 | 中国科学院大连化学物理研究所 | Catalyst for reaction of alpha-olefines prepared through ether cracking |
| EP0925831A2 (en) | 1997-12-23 | 1999-06-30 | China Petrochemical Corporation | Pillared clay catalyst for catalytic cracking of heavy oil, method for preparation and use thereof |
| US6416656B1 (en) | 1999-06-23 | 2002-07-09 | China Petrochemical Corporation | Catalytic cracking process for increasing simultaneously the yields of diesel oil and liquefied gas |
| CN100464847C (en) * | 2004-03-10 | 2009-03-04 | 中国科学院大连化学物理研究所 | Composite zeolite catalyst for preparing alcohol and ether compounds and preparation thereof |
| CN1301794C (en) * | 2004-08-06 | 2007-02-28 | 董家禄 | Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process |
| CN100406416C (en) * | 2006-07-03 | 2008-07-30 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
| CN101116827B (en) * | 2006-07-31 | 2010-12-01 | 中国石油化工股份有限公司 | Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking and its uses |
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| US8716163B2 (en) | 2006-08-31 | 2014-05-06 | China Petroleum & Chemical Corporation | Hydrocarbon conversion catalyst |
| US8900445B2 (en) | 2006-08-31 | 2014-12-02 | China Petroleum & Chemical Corporation | Process for the catalytic conversion of hydrocarbons |
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| CN116239467A (en) * | 2022-12-13 | 2023-06-09 | 南通宝凯药业有限公司 | Preparation method of high-purity difluoroethyl acetate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1034586C (en) | Catalytic conversion method of low-carbon olefines high-output | |
| CN1034223C (en) | Cracking catalyst for processing low-carbon olefines | |
| CN1085885A (en) | The catalysis conversion method of petroleum hydrocarbon | |
| CN1043520A (en) | A kind of catalyst for cracking of producing low-carbon alkene | |
| CN1872957A (en) | Method for catalytic cracking petroleum hydrocarbons | |
| CN1955260A (en) | Hydrocracking method | |
| CN1056514A (en) | Catalyst for hydrogenation treatment of heavy fraction oil | |
| CN1102634C (en) | Catalyst for catalytic thermal cracking process to prepare lower olefine | |
| CN1042201C (en) | Cracking catalyst of rich producing olefines | |
| CN1069513A (en) | Catalyst for heavy oil catalytic cracking and preparation method thereof | |
| CN1064072C (en) | Catalyst containing modified kaoling for cracking hydrocarbons | |
| CN1072032C (en) | Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene | |
| CN1234806C (en) | Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene | |
| CN1031030A (en) | The preparation of low content of rare earth super-stable Y molecular sieves | |
| CN1065903C (en) | Process for synchronously preparing low-carbon olefines and high aromatic-hydrocarbon gasoline | |
| CN1297018A (en) | Catalytic cracking catalyst for preparing light oil with high yield and its preparing process | |
| CN1055105C (en) | Cracking catalyst for high yield of isobutene and isopentene | |
| CN1065900C (en) | Process for catalytic aromatization of gasoline fraction | |
| CN1048428C (en) | Multi-zeolite catalyzer for preparation of low-carbon olefines | |
| CN1031409C (en) | Assistant for increasing octane value of gasoline and yield rate of propene and butene | |
| CN1232070A (en) | Catalytic conversion method for preparing propylene, isobutane and isoalkane-enriched gasoline | |
| CN1053918C (en) | Double zeolite catalyst for prepn. of low carbon olefine | |
| CN1052133A (en) | Assisted catalyst for catalyzing cracking with high octane number | |
| CN1055302C (en) | Cracking catalyst containing natural zeolite | |
| CN1955259A (en) | Parallel 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 |