CN1037327C - Splitting catalyst containing high-silicon zeolite - Google Patents
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- CN1037327C CN1037327C CN90104293A CN90104293A CN1037327C CN 1037327 C CN1037327 C CN 1037327C CN 90104293 A CN90104293 A CN 90104293A CN 90104293 A CN90104293 A CN 90104293A CN 1037327 C CN1037327 C CN 1037327C
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Abstract
The present invention relates to a cracking catalyst containing high-silicon zeolite, which is composed of 10 to 30 wt% of modified high-silicon zeolite and 70 to 90 wt% ofcarrier, wherein the modified high-silicon zeolite contains 0.01 to 3.0 wt% of phosphorus, 0.01 to 1.0 wt% of ferrum or 0.01 to 10 wt% of aluminum (excluding aluminum in the zeolite structure), ZSM molecular sieves of which the ratio of silicon to aluminum is greater than 15 to 1, and beta zeolite or mordenite; the carrier is an inorganic oxide, or a mixture of the inorganic oxide and kaoline. The cracking catalyst is used for the catalytic cracking process of hydrocarbons and has high catalytic cracking activity.
Description
The present invention relates to a kind of catalyst for cracking, specifically relate to a kind of catalyst for cracking that contains silica-rich zeolite.
Low-carbon alkene is an important chemical material, and can adopt with natural gas, naphtha or light diesel fuel is that the thermal cracking of raw material and the methods such as heat carrier cracking of heavy hydrocarbon prepare; Conventional catalytic cracking unit when producing gasoline and diesel oil, also by-product low-carbon alkene, but olefin yields is lower.
Many patent introduction catalytic thermal cracking method are produced low-carbon alkene from hydrocarbon raw material.Their use metal load type catalyst or solid acid catalyst, and DD-152 for example introduces in 356 patents and uses amorphous aluminum silicide to make catalyst to produce low-carbon alkene; JP60-224, having adopted in 428 patents with the ZSM-5 molecular sieve is that active component and aluminium oxide are the catalyst of carrier, under 600-750 ℃ of reaction temperature, carries out C
5-C
25The catalytic cracking reaction of paraffin hydrocarbon raw material, C
2-C
4Olefin yields is about 30%.When adopting above-mentioned technology, the reaction temperature height requires high to equipment material.
On the basis of existing technology, the purpose of this invention is to provide and a kind ofly can improve productivity of low carbon olefin hydrocarbon, and the catalyst for cracking that contains silica-rich zeolite of double steam oil and diesel oil.
Catalyst provided by the invention is made up of the modification silica-rich zeolite of the heavy % of 10-30 and the carrier of the heavy % of 70-90.The modification silica-rich zeolite is for containing the heavy % phosphorus of (is benchmark with zeolite weight) 0.01-3.0, the heavy % iron of 0.01-1.0 or the heavy % aluminium of 0.01-10 (do not comprise zeolite structured in aluminium), its framework si-al ratio greater than 15, preferably the ZSM molecular sieve of 50-150, β zeolite or modenite.Carrier is a kind of inorganic oxide or above-mentioned inorganic oxide and kaolinic mixture that comprises aluminium oxide, silica, silica-aluminium oxide, silica-magnesia, silica-zirconia.
Catalyst provided by the invention can be prepared by following method:
(1) compound concentration is 0.01-0.2M, preferably the halid aqueous solution of the aluminium of 0.05-0.08M; Concentration is 0.01-0.1M, preferably the ferric halide solution of 0.02-0.07M; Concentration is preferably ferrous halide solution of 0.008-0.02M of 0.005-0.03M; Perhaps concentration is 0.01-0.2M, the saline solution of ammonium phosphate of best 0.05-0.1M, and the pH value of solution is 2.5-4.2.
(2) with silica alumina ratio greater than 15, preferably the Hydrogen of 50-150 or potassium type ZSM molecular sieve, β zeolite or modenite are heated to 350-820 ℃, preferably 500-780 ℃, with 0.1-10 hour
-1, preferably 1-5 hour
-1Volume space velocity feed the solution select from (1) gained, handled 0.5-20 hour, best 1-5 hour, promptly get the silica-rich zeolite of modification.
(3) be carrier with kaolin, aluminium oxide, silica, silica-aluminium oxide, silica-magnesia, silica-zirconia or its precursor, with Ludox, aluminium colloidal sol, silicon-aluminum sol, silica-alumina gel or boehmite is bonding agent, in molecular sieve: the ratio of carrier: bonding agent=10-30: 65-85: 1-10 (weight ratio),, get product with (2) gained molecular sieve, carrier with bonding agent mixes, moulding, drying according to the conventional preparation method of Cracking catalyst.
Described ammonium phosphate salt can be ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP).
Described (1) gained solution preferably gives earlier feeding after heat is vaporized again and is equipped with in the reactor of zeolite.
The precursor of described inorganic oxide can be its corresponding hydroxide, boehmite, Ludox, aluminium colloidal sol, silicon-aluminum sol or gel etc.
Catalyst provided by the invention is compared with the existing catalyst that contains unmodified silica-rich zeolite, has advantages of high catalytic activity, yield of light olefins, gasoline and diesel yield are higher, and the acidity of active component silica-rich zeolite is eager to excel than the acidity of unmodified silica-rich zeolite in the catalyst of the present invention.
Below will the present invention will be further described with embodiment.
Example 1-3
Prepare 400 milliliters of AlCl
3The aqueous solution is broken into the fine powder that particle diameter is the 0.5-2 millimeter with 60 gram HZSM-5 (silica alumina ratio is 80.5, and dying of Shanghai seven factories produce), and the reactor of packing into is warming up to uniform temperature, adds above-mentioned AlCl with certain air speed
3Solution behind the processing certain hour, promptly gets modified molecular screen a, b and c.The detail operations condition sees Table 1.
Table 1
*For infiltrating the amount of the aluminium of molecular sieve after handling through modification.
| Example (molecular sieve numbering) | AlCl solution | Treatment temperature ℃ | Processing time hour | The air speed that solution adds, hour -1 | Molecular sieve contains the Al amount *, heavy % | |
| Concentration M | PH value | |||||
| 1(a) 2(b) 3(c) | 0.02 0.05 0.085 | 3.45 3.36 3.22 | 760 800 550 | 4 3.5 9 | 1.7 1.9 0.75 | 0.4 1.7 6.1 |
Example 4
Add 1.8 milliliters of SPAs (concentration is 85 heavy %) in (1) 400 ml water, add 5 milliliters of concentrated ammonia liquors (concentration is 28 heavy %), mix, the pH value of solution is 3.1.
(2) 25 gram HZSM-5 molecular sieves (identical with example 1) are packed in the reactor, are heated to 750 ℃, with 4.0 hours
-1Volume space velocity add (1) solution, handled 4 hours, promptly get the molecular sieve d of phosphorous 1.06 weight %.
Example 5
Add 1.2 gram frerrous chlorides in (1) 400 ml water, it is stand-by to filter rear filtrate, and its pH value is 2.9.
(2) get 30 gram HZSM-5 molecular sieves (identical) and pack in the reactor, be warming up to 740 ℃, with 2.7 hours with example 1
-1Volume space velocity add (1) gained solution, handled 4 hours, promptly get the HZSM-5 molecular sieve e of iron content 0.25 weight %.
Example 6
In (1) 400 milliliter of decationized Y sieve water, add 3 gram FeCl
36H
2O crystal, the pH value of gained solution are 2.75.
(2) get 25 gram HZSM-5 molecular sieves (identical) and pack in the reactor, be warming up to 760 ℃, with 4.0 hours with example 1
-1Volume space velocity add (1) gained solution, handled 4 hours, promptly get the HZSM-53 molecular sieve f of iron content 0.29 weight %.
Example 7
(silica alumina ratio is 25.8 to get 100 gram HZSM-5, synthetic with reference to the USP4578371 method) add in the KCl aqueous solution that 300 ml concns are 10 heavy %, under 90 ℃, carry out ion-exchange reactions, react after 1 hour, filter, washing, repeated exchanged, filtration, washing be once as stated above again, drying is 2 hours under 120 ℃, promptly gets the KZSM-5 molecular sieve.
Get the above-mentioned KZSM-5 molecular sieve of 30 grams and carry out modification processing, just FeCl by the method for example 5
2Solution concentration is 0.02M, promptly gets the KZSM-5 molecular sieve g of iron content 0.12 heavy %.
Example 8
Get KZSM-5 molecular sieve 30 grams of example 7 gained, carry out modification by the method for example 6 and handle, just FeCl
3Solution concentration is 0.08M, promptly gets the KZSM-5 molecular sieve h of iron content 0.31 heavy %.
Example 9
Get 60 gram Na zeolite betas (Fushun No.3 Petroleum Factory produces, and its silica alumina ratio is 26.8), adding concentration is the NH of 10 heavy %
4In the Cl solution, under 90 ℃, carry out ion-exchange reactions, filter after 1 hour, wash to there not being Cl
-Ion, repeated exchanged, filtration, washing are three times again, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours, Hydrogen β zeolite.
By the method for example 2 above-mentioned H type β zeolite is carried out modification and handle, promptly get the H β zeolite i that contains the heavy % of Al2.1 (do not comprise zeolite structured in aluminium).
Example 10
Get the prepared molecular sieve a-1100 gram of example 1-9 respectively, add 400 gram boehmites (butt, the Chang Ling oil plant is produced) and low amounts of water mixing, add 25 gram Ludox again and (contain SiO
220 heavy %, school-run workshop produces in Beijing three) mix thoroughly after, in 120 ℃ dry 4 hours down, compression molding, be broken into 20-40 order fine grained, promptly get the catalyst A-I that contains modification silica-rich zeolite 19.8 heavy % and carrier 80.2 heavy %.
Example 11
Get example 6 gained molecular sieve f25 grams (butt), add kaolin (the Suzhou machine selects 2#) 70 grams, add SB alumina powder (Germany import) 5 grams (butt) again, add 1.2 milliliters of hydrochloric acid solutions (concentrated hydrochloric acid and water volume ratio 1: 1) and low amounts of water, mix, kept 8 hours down at 60-70 ℃, 120 ℃ of dryings 4 hours, moulding is broken into 20-40 order particle, promptly gets catalyst J.
Example 12
Get example 5 gained molecular sieve e15 gram, add α-Al
2O
3(1000 ℃ of roastings of boehmite 4 hours, Chang Ling oil plant) 78 gram adds Ludox (identical with silicon solution in the experiment 10) 35 grams, mixes, and 120 ℃ of dryings 6 hours, moulding promptly gets catalyst k.Comparative Examples
Get 20 gram HZSM-5 molecular sieves (identical with example 1), press example 1 method and handle, just water replaces AlCl
3The aqueous solution promptly gets and contrasts molecular sieve.
Get 20 gram HZSM-5 molecular sieves and 80 gram α-Al
2O
3(same with example 12) mixes, and promptly gets comparative catalyst x.
Example 13
Make ammonia adsorption/desorption method and measure the acidity of molecular sieve active component in the catalyst of the present invention, the results are shown in Table 2.
Table 2
| Molecular sieve | |
| Acid (millivolt) | A b c d e f g h i contrast |
| H 0 H 2 H 5 H 10 | 120 261 247 213 237.5 243.0 248.0 260.0 271.0 77 47 121 135 325 32.5 27.0 31 25.5 109.0 28 40 108 119 30 30.5 24.0 25.5 23 98.0 18 31 75 105 27.5 27.5 21.0 25.0 20 77.0 13 |
H
0Adsorb NH after representing adsorption equilibrium
3Amount, H
2After representing balance, desorption is molecular sieve adsorption NH in the time of 2 minutes
3Amount, H
5And H
10Then be respectively molecular sieve adsorption NH after desorption 5 and the 10 fens kinds
3Amount.
As seen from the table, the contained modification silica-rich zeolite of catalyst of the present invention has the acidity that higher unmodified silica-rich zeolite is eager to excel.
Example 14
On the pulse micro-inverse device, with pure hydrocarbon n-C
14(Qilu Petroleum Chemical Corporation Institute's catalyst plant is produced to come evaluate catalysts A-C, E-I and CHP industrial crack catalyst, contain the heavy % of ZSM-520, kaolin 75 heavy %, aluminium oxide 5 heavy %) catalytic activity, reaction condition is: catalyst loading amount 0.2 gram, 480 ℃ of reaction temperatures, sample size 0.2 μ l, reaction result sees Table 3.
Table 3
| Catalyst | A B C E F G H I CHP |
| The heavy % of cracking conversion ratio | 60.5 62.5 58.3 45.0 42.8 47.0 43.9 61.5 32.8 |
As known from Table 3, catalyst provided by the invention has the catalytic pyrolysis activity higher than existing catalyst for cracking.
Example 15
On atmospheric fixed bed reactor, with the triumph subtract one and the second line of distillation mixed gatch be the catalytic activity that raw material (330 ℃-510 ℃ of boiling ranges) comes evaluate catalysts B-I, CHP and comparative catalyst X.Reaction condition is: 560 ℃ of reaction temperatures, weight space velocity 2.8 hours
-1, catalystoil ratio 2.2,15 gram reaction results see Table 4 during the catalyst dress.
Table 4
| The catalyst product yield | B C D E F G H I J K CHP X |
| Gasoline, heavy % diesel oil, heavy % gasoline+diesel oil | 15.4 9.6 9.6 12.6 12.1 11.8 12.0 14.5 12.8 9.5 8.3 8.5 5.1 4.1 3.6 5.9 5.5 6.2 5.2 5.5 5.8 4.5 3.1 3.0 20.5 13.7 13.2 18.5 17.6 18.0 17.2 20.0 18.6 14.0 11.4 11.5 |
| C 2 ＝, body % C 3, body % C 4 ＝, body % C 2 ＝-C 4 ＝ | 19.7 20.8 19.2 21.2 20.5 21.5 21.9 19.5 22.0 19.8 18.8 18.5 10.0 10.9 10.2 12.1 11.9 12.0 12.4 10.8 12.5 10.7 9.0 9.7 3.3 3.8 3.4 4.6 5.0 4.3 4.5 3.5 5.2 3.5 2.7 2.3 33.0 35.5 32.8 37.9 37.4 37.8 38.8 33.8 39.7 34.0 30.5 30.5 |
| Coke, heavy % | 3.16 3.41 2.31 1.96 1.84 1.91 1.60 2.52 1.94 1.44 3.97 2.81 |
Gasoline is 60-200 ℃ cut, and diesel oil is 200-330 ℃ of cut.
Catalyst provided by the invention as can be seen from Table 4 has comparison than catalyst and the high activity of CHP catalyst for cracking, and its gasoline, diesel oil and yield of light olefins are higher, and the coke content on most of catalyst is lower.
Claims (6)
1. catalyst for cracking that contains the ZSM-5 zeolite, it is characterized in that forming by the modified ZSM-5 zeolite of 10～30 heavy % and the carrier of 70～90 heavy %, modified ZSM-5 zeolite is to contain that to account for zeolite weight 0.01～1.0 heavy % iron, framework si-al ratio be 50～150 ZSM-5 zeolite, and carrier is a kind of inorganic oxide or above-mentioned inorganic oxide and kaolinic mixture that is selected from aluminium oxide, silica, silica-alumina.
2. catalyst according to claim 1 is characterized in that this Preparation of catalysts method is:
(1) compound concentration is the ferric halide solution of 0.01～0.1M or ferrous halide solution that concentration is 0.005～0.03M, and the pH value of solution is 2.5～4.2;
(2) be that 50～150 Hydrogen or potassium type ZSM-5 zeolite are heated to 350～820 ℃ with silica alumina ratio, with 0.1～10 hour
-1Volume space velocity feed (1) gained solution, handled 0.5～20 hour;
(3) be carrier with kaolin, aluminium oxide, silica, silica-alumina or its precursor, with Ludox, aluminium colloidal sol, silicon-aluminum sol, silica-alumina gel or boehmite is bonding agent, press zeolite: carrier: bonding agent=10～30: 65～85: 1～10 weight ratio, carrier, bonding agent and (2) gained zeolite are mixed moulding, drying according to the conventional preparation method of Cracking catalyst.
3. catalyst according to claim 2 is characterized in that said ferric halide solution concentration is 0.02～0.07M.
4. catalyst according to claim 2 is characterized in that said ferrous halide solution concentration is 0.008～0.02M.
5. catalyst according to claim 2, the treatment temperature that it is characterized in that said ZSM-5 zeolite is 500～780 ℃, the volume space velocity that adds said (1) gained solution is 1～5 hour
-1, the processing time is 1～5 hour.
6. catalyst according to claim 2 is characterized in that the precursor of said inorganic oxide is its corresponding hydroxide, boehmite, Ludox, aluminium colloidal sol and silicon-aluminum sol or gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90104293A CN1037327C (en) | 1990-06-20 | 1990-06-20 | Splitting catalyst containing high-silicon zeolite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90104293A CN1037327C (en) | 1990-06-20 | 1990-06-20 | Splitting catalyst containing high-silicon zeolite |
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|---|---|
| CN1057408A CN1057408A (en) | 1992-01-01 |
| CN1037327C true CN1037327C (en) | 1998-02-11 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069535A1 (en) * | 2004-12-28 | 2006-07-06 | China Petroleum & Chemical Corporation | A catalyst and a hydrocarbon oil cracking method |
| CN100439476C (en) * | 2001-10-04 | 2008-12-03 | 康斯乔最高科学研究公司 | Use of zeolite itq-21 in the catalytic cracking of organic compounds |
| RU2709522C1 (en) * | 2019-09-16 | 2019-12-18 | Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") | Catalyst for joint cracking of petroleum fractions |
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| CN1073540C (en) * | 1998-11-26 | 2001-10-24 | 中国石油化工集团公司 | Catalysis process for preparing light olefin from low-carbon paraffin |
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| EP0134327A1 (en) * | 1981-12-22 | 1985-03-20 | Mobil Oil Corporation | Treatment of zeolites |
| US4584091A (en) * | 1984-12-13 | 1986-04-22 | Exxon Research And Engineering Co. | Cracking with co-matrixed zeolite and p/alumina |
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1990
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Patent Citations (3)
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|---|---|---|---|---|
| EP0134327A1 (en) * | 1981-12-22 | 1985-03-20 | Mobil Oil Corporation | Treatment of zeolites |
| US4584091A (en) * | 1984-12-13 | 1986-04-22 | Exxon Research And Engineering Co. | Cracking with co-matrixed zeolite and p/alumina |
| EP0188841A1 (en) * | 1984-12-21 | 1986-07-30 | Catalysts & Chemicals Industries Co., Ltd. | Hydrocarbon catalytic cracking catalyst compositions and method therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100439476C (en) * | 2001-10-04 | 2008-12-03 | 康斯乔最高科学研究公司 | Use of zeolite itq-21 in the catalytic cracking of organic compounds |
| WO2006069535A1 (en) * | 2004-12-28 | 2006-07-06 | China Petroleum & Chemical Corporation | A catalyst and a hydrocarbon oil cracking method |
| RU2709522C1 (en) * | 2019-09-16 | 2019-12-18 | Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") | Catalyst for joint cracking of petroleum fractions |
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| Publication number | Publication date |
|---|---|
| CN1057408A (en) | 1992-01-01 |
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