CN1261218C - Hydrocarbon desulfurizer - Google Patents
Hydrocarbon desulfurizer Download PDFInfo
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- CN1261218C CN1261218C CN 03153767 CN03153767A CN1261218C CN 1261218 C CN1261218 C CN 1261218C CN 03153767 CN03153767 CN 03153767 CN 03153767 A CN03153767 A CN 03153767A CN 1261218 C CN1261218 C CN 1261218C
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Abstract
The present invention relates to a hydrocarbon-oil desulfurizer containing 15 to 60 wt% of Y type zeolite modified by phosphorus and containing rare earth, 10 to 60 wt% of inorganic oxide and 0 to 75 wt% of clay by catalyst weight, wherein the Y type zeolite modified by phosphorus and containing rare earth contains phosphorus accounting for 0.5 to 8 wt% of the zeolite measured by P2O5 and rare earth accounting for 18 to 35 wt% of the zeolite measured by RE2O3. The proportion of silicon to aluminum in the zeolite is lower than 6.
Description
Technical field
The invention belongs to the refining of hydrocarbon ils under the situation that does not have hydrogen, more particularly, is a kind of desulfurizing agent that reduces content of sulfur in gasoline.
Background technology
Along with the increase of sour crude working ability, the also corresponding increase of the sulfur content in the oil product, environmental pollution increases the weight of, and has caused the common concern of various countries.For limiting gasoline sulfure content less than 50ppm, diesel oil specification control index is that restriction diesel oil sulfur content (mass fraction) is less than 0.05 heavy % to specification gasoline control index in developed country.China at present to the requirement of gasoline products sulfur content less than 800ppm, diesel product sulfur content less demanding, but, also require more and more higher to gasoline and the control of diesel oil sulfur content specification along with the environmental protection increasingly stringent in 0.2 heavy %.Is to adopt hydrofinishing or hydro-upgrading to reducing gasoline and diesel oil sulfur content than effective method, under hydrogen pressure, realize the catalytic reforming of diesel oil by hydrofinishing or hydro-upgrading, reach desulfurization, denitrogenation, alkene is saturated, aromatic hydrocarbons is saturated purpose, to improve gasoline and diesel quality, satisfy environmental requirement.But this method relative cost is higher, and simultaneously, present most oil refining enterprises are not the means that lack hydrofinishing and hydro-upgrading, is exactly the not enough or shortage hydrogen source of disposal ability of hydrofinishing and hydro-upgrading.
Adopt hydrofinishing or hydrogenation modification method can reduce content of sulfur in gasoline, but the octane number of gasoline also can descend to some extent simultaneously.For this reason, USP 5,843, and 300 and USP5,935,422 disclose and use adsorbent to remove the method for the sulphur in the gasoline.Adsorbent is X or the Y zeolite that contains alkali metal or alkaline-earth metal, and flood the group VIII metal of the heavy % of a kind of 0.05-1.0 of containing, in temperature is 25-200 ℃, sulphur in the light distillates such as adsorbed gasoline under enough adsorption times, kerosene, sulphur in these light distillates can be dropped to below the 100ppm, then, the adsorbent of adsorption of sulfur compounds is 25-300 ℃ in temperature, with hydrogen regeneration, the adsorbent after the regeneration adsorbs the sulphur in the light distillate again under the time enough.But the required time of this method is longer, needs simultaneously to regenerate with hydrogen.
CN1286291A discloses the catalytic cracking and desulfurizing catalyst that is used for refining light oil products, this catalyst mainly be with the dipping rare earth element the stronger molecular sieve of acidity be active component, be carrier with the burning that sulfide is had stronger selection adsorptivity effect.This catalyst desulfurizing rate is below 70%.
CN1064499A discloses a kind of catalyst and cracking of hydrocarbon of the REY of containing molecular sieve, be that REY molecular sieve with the heavy % of 5-25 is an active component, be aided with the amorphous aluminum silicide of the heavy % of 75-95 or contain the clay of al binder and constitute, wherein REY molecular sieve middle rare earth content (RE
2O
3Meter) is the heavy % of 12-16.
CN1217231A discloses a kind of phosphorous faujasite hydrocarbon cracking catalyzer, and it is the heavy % of heavy %, clay 0-75 of heavy %, al binder 10-60 of heavy %, rare earth oxide 0.1-40 of faujasite 10-60 heavy %, phosphorus 0.01-1.5 of benchmark that this catalyst contains with the catalyst weight.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of desulfurizing agent that reduces the sulfur content in the gasoline.
Desulfurizing agent provided by the invention contain with the catalyst weight be benchmark contain the heavy % of rare earth Y type zeolite 15-60 heavy %, inorganic oxide 10-60 heavy %, clay 0-75 through the phosphorus modification; The wherein said rare earth Y type zeolite that contains through the phosphorus modification contains with P
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 0.5-8 of meter, with RE
2O
3The rare earth that accounts for the heavy % of this zeolite weight 18-35 of meter, and the silica alumina ratio of this zeolite is less than 6.
Compared with prior art, desulfurizing agent provided by the present invention has higher sour density, more even and more weak acid strength and higher hydrothermal stability, suppresses the cracking of gasoline fraction, helps removing the sulfur-nitrogen compound in the gasoline.
The specific embodiment
Desulfurizing agent provided by the invention contain with the catalyst weight be benchmark contain the heavy % of rare earth Y type zeolite 15-60 heavy %, inorganic oxide 10-60 heavy %, clay 0-75 through the phosphorus modification.The rare earth Y type zeolite that contains through the phosphorus modification of the present invention contains with P
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 0.5-8 of meter, with RE
2O
3The rare earth that accounts for the heavy % of this zeolite weight 18-35 of meter, and the silica alumina ratio of this zeolite is less than 6.
Desulfurizing agent provided by the present invention preferably contain with the catalyst weight be benchmark contain the heavy % of rare earth Y type zeolite 20-55 heavy %, inorganic oxide 10-60 heavy %, clay 0-65 through the phosphorus modification.Further preferably contain with the catalyst weight be benchmark contain the heavy % of rare earth Y type zeolite 30-50 heavy %, inorganic oxide 10-60 heavy %, clay 5-60 through the phosphorus modification.
The rare earth Y type zeolite that contains through the phosphorus modification of the present invention is selected from: the mixture of one or more among REY, REHY, the REUSY, wherein, preferred REY and/or REHY, most preferably REY.
The silica alumina ratio of zeolite of the present invention is less than 6, and preferred silica alumina ratio is less than 5.
Of the present invention through the phosphorus modification contain rare earth Y type zeolite contain account for the heavy % of zeolite weight 18-35 rare earth oxide (with RE
2O
3Meter), the heavy % of preferred 20-35, the most preferably heavy % of 25-35.Described rare earth oxide can be the mixed rare-earth oxide of rich lanthanum or rich cerium, also can be the single oxide of elements such as lanthanum, cerium, the mixed rare-earth oxide of preferred rich lanthanum or rich cerium.
The rare earth Y type zeolite that contains through the phosphorus modification of the present invention contains with P
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 0.5-8 of meter is preferably with P
2O
5The phosphorus content of meter is the heavy % of 1-7, most preferably with P
2O
5The phosphorus content of meter is the heavy % of 2-6.
Inorganic oxide of the present invention is selected from amorphous silicon aluminium, aluminium oxide and/or silica.
Clay of the present invention is the various clays that are commonly used for catalyst substrates, as one or more the mixture in kaolin, halloysite, imvite, bentonite, the sepiolite, and preferred kaolin.
The preparation method of desulfurizing agent provided by the invention is as follows: the precursor of inorganic oxide being mixed with the clay predetermined amounts and with decationized Y sieve water it is mixed with solid content is the slurries that 10-50 weighs %, with inorganic acid its pH is regulated and is maintained until 2-4, the zeolite that after leaving standstill aging 0-2 hour under 20-80 ℃, adds scheduled volume, homogeneous, spray shaping, washing are removed free Na
+, drying.
The precursor of wherein said inorganic oxide is selected from: aluminium colloidal sol, boehmite, Ludox and composition thereof and silicon-aluminum sol or gel, be preferably the aging boehmite and the mixture of aluminium colloidal sol, the aging boehmite and the weight ratio (in aluminium oxide) of aluminium sol adhesive are 0.1-10, preferred 0.5-7.0.
Described aging boehmite slurries can prepare according to a conventional method, as can be with the making beating of boehmite and water, after stirring, its PH is regulated and be maintained until 2-4 with inorganic acid, leave standstill under 20-80 ℃ aging 0-2 hour, are prepared into aging boehmite.
Described inorganic acid is selected from any one or more than one the mixture in hydrochloric acid, nitric acid, phosphoric acid or the sulfuric acid.
The described zeolite that contains rare earth can fully exchange the zeolite and the aqueous solution that contains rare earth ion, and promptly ion exchange process repeats repeatedly, and for example, exchange makes molecular sieve of the present invention more than 2 times; Also zeolite can be carried out NH earlier
4 +Ion-exchange exchanges and makes with the aqueous solution that contains rare earth ion again, also can directly be purchased and obtains.
The aqueous solution of described rare earth ion is the water-solubility rare-earth compound, as rare earth chloride, rare earth nitrades etc., and preferred rare earth chloride.
In the preparation method of desulfurizing agent provided by the present invention, with the aqueous solution of above-mentioned rare earth Y type zeolite and phosphorus-containing compound evenly, left standstill 0-8 hour, drying more than 0.5 hour, makes phosphorous rare earth Y type zeolite in 450-600 ℃ of following roasting.The aqueous solution of above-mentioned rare earth Y type zeolite and phosphorus-containing compound evenly, leave standstill, can under 0-100 ℃, carry out, preferably under 0-40 ℃, carry out, more preferably at room temperature carry out.Described phosphorus-containing compound is phosphorous water soluble compound, it is selected from one or more the mixture in orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium phosphite, more preferably phosphoric acid ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).
The aqueous solution of zeolite of the present invention and phosphorus-containing compound, when zeolite is two or more, preferably with different zeolites respectively with the aqueous solution of phosphorus-containing compound.
Desulfurizing agent provided by the invention is applicable to the desulfurization of light-end products such as gasoline, diesel oil in the catalytic conversion process.
The following examples will be further specified the present invention, but therefore the present invention is not subjected to any restriction.
The preparation method of employed rare earth Y type zeolite through the phosphorus modification is as follows among the embodiment: with commercially available REY zeolite (Qilu Petrochemical company catalyst plant product, silica alumina ratio 2.0) according to zeolite: ammonium nitrate: the weight ratio of deionized water=1: 1: 20 was 90 ℃ of following ion-exchanges 2 hours, filter washing back repeated exchanged and once obtain ammonium type REY, its Na
2O content is not more than 0.15 heavy %.Ammonium type zeolite and the solution that is mixed with by phosphoric acid and deionized water are mixed by the solid weight ratio of 2: 1 water, at room temperature stirred dipping 2 hours, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours.What so make contains P
2O
51.5 heavy %, RE
2O
317.5 the REY zeolite of heavy %, note is made zeolite PREY-1; What make contains P
2O
52.1 heavy %, RE
2O
317.5 the REY zeolite of heavy % note is made zeolite PREY-2; What make contains P
2O
53.9 heavy %, RE
2O
317.3 the REY zeolite of heavy % note is made zeolite PREY-3.
With 34.36 kilograms of decationized Y sieve water with 13.5 kilograms of halloysites (Suzhou china clay company industrial products, solid content is 73 heavy %) making beating, add 13.5 kilograms of boehmites (Shandong Zibo aluminium manufacturer industrial products again, solid content is 64 heavy %) and 1.17 liter hydrochloric acid (concentration is 30 weight %) stir, under 75 ℃, left standstill aging 1 hour, keep pH2-4, be cooled to 60 ℃, adding the PREY-1 for preparing in advance, the PREY-2 and the PREY-3 zeolite that account for desulfurizing agent weight 30 heavy % respectively fully mixes, spray drying forming, washing are removed free Na
+, be drying to obtain desulfurizing agent sample P DS1, PDS2 and PDS3.
Desulfurizing agent sample P DS1, PDS2 and PDS3 are designated as APDS1, APDS2 and APDS3 through 4 hours resulting desulfurizing agents of 800 ℃ of 100% steam aging.
Contrast medium in the Comparative Examples is prepared as commercially available REY zeolite (Qilu Petrochemical company catalyst plant product, silica alumina ratio 2.0) according to zeolite: ammonium nitrate: the weight ratio of deionized water=1: 1: 20 was 90 ℃ of following ion-exchanges 2 hours, filter washing back repeated exchanged and once obtain ammonium type REY, its Na
2O content is not more than 0.15 heavy %.At room temperature stirred dipping 2 hours, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours.What make contains RE
2O
317.5 the REY zeolite of heavy % note is made zeolite REY-2.With 34.36 kilograms of decationized Y sieve water with 13.5 kilograms of halloysites (Suzhou china clay company industrial products, solid content is 73 heavy %) making beating, add 13.5 kilograms of boehmites (Shandong Zibo aluminium manufacturer industrial products again, solid content is 64 heavy %) and 1.17 liter hydrochloric acid (concentration is 30 weight %) stir, under 75 ℃, left standstill aging 1 hour, keep pH2-4, be cooled to 60 ℃, adding the REY-2 zeolite for preparing in advance that accounts for desulfurizing agent weight 30 heavy % respectively fully mixes, spray drying forming, washing are removed free Na
+, the thousand dry desulfurizing agent sample DS2 that promptly get.
Contrast medium sample DS2 is designated as ADS2 through 4 hours resulting desulfurizing agents of 800 ℃ of 100% steam aging.
Embodiment 1-2
These embodiment explanation: provided by the invention with the clay be matrix, boehmite be binding agent single zeolite desulfurizing agent preparation and on micro-reactor continuously, investigate the performance of these desulfurizing agents.
The heavy petrol (sulfur content is 1844.9mg/L) that with the boiling range is 90-202 ℃ is reaction raw materials, respectively desulfurizing agent PDS2 and APDS2 are being carried out evaluation test on the micro-reactor continuously, experimental condition is desulfurizing agent loading amount 5.0 grams, 350 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 4 hours
-1, the agent weight of oil is than 10.Table 1 has been listed reaction result.
Comparative Examples 1-2
The heavy petrol (sulfur content is 1844.9mg/L) that with the boiling range is 90-202 ℃ is reaction raw materials, respectively corresponding contrast medium DS2 and ADS2 are being carried out evaluation test on the micro-reactor continuously, experimental condition is desulfurizing agent loading amount 5.0 grams, 350 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 4 hours
-1, the agent weight of oil is than 10.Reaction result is also listed in table 1.
As can be seen from Table 1, embodiment 1 is with respect to Comparative Examples 1, and desulfurization degree is lower than Comparative Examples 1, but two kinds of desulfurizing agents are after steam treatment, and the desulfurizing agent desulfurization degree that phosphorus was handled descends less, sees embodiment 2, more without the desulfurizing agent desulfurization degree decline that phosphorus was handled, see Comparative Examples 2.
Embodiment 3-4
The heavy petrol (sulfur content is 1844.9mg/L) that with the boiling range is 90-202 ℃ is reaction raw materials, respectively desulfurizing agent PDS1 and PDS3 are being carried out evaluation test on the micro-reactor continuously, experimental condition is desulfurizing agent loading amount 5.0 grams, 350 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 4 hours
-1, the agent weight of oil is than 10.Table 2 has been listed reaction result.
As can be seen from Table 2, the desulfurizing agent phosphorus compound that contains appropriate amount helps desulfurized effect.
Table 1
| Gasoline stocks | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Comparative Examples 2 | |
| Desulfurizing agent | PDS-2 | DS-2 | APDS-2 | ADS-2 | |
| Chromatogram sulphur, mg/L | |||||
| Ethanol sulphur | 5 | 6.2 | 5.9 | 6.0 | 5.3 |
| N-propyl mercaptan | 5 | 7.3 | 6.3 | 7.5 | 6.4 |
| Thiophene | 40.3 | 33.3 | 32.2 | 34.6 | 35.3 |
| N-butyl mercaptan | 5.5 | 2.6 | 2.4 | 2.8 | 3 |
| The 2-methylthiophene | 211 | 48.1 | 43.2 | 55 | 60.6 |
| 3 methyl thiophene | 261 | 43.2 | 37.3 | 47.1 | 57 |
| Thiophane | 40.6 | 22.5 | 20.5 | 26 | 32.5 |
| 2-methyl thiophane | 38 | 31 | 25.4 | 32.4 | 37.9 |
| Ethylthiophene | 98 | 43.2 | 38 | 46.5 | 51.5 |
| 2, the 5-thioxene | 60 | 21 | 13 | 23 | 15.6 |
| Carbon six mercaptan | 6 | 2.6 | 1.3 | 2.5 | 2 |
| 2, the 4-thioxene | 156 | 13.8 | 11 | 15.2 | 13.5 |
| Carbon six thioethers | 11 | 3.7 | 3 | 3.5 | 3.7 |
| 2, the 3-thioxene | 218 | 7 | 3.5 | 5.3 | 14.0 |
| 3, the 4-thioxene | 52 | 1.6 | 1.5 | 0.7 | 1.5 |
| 3,3-dimethyl tetrahydro thiophene | 5 | 0.2 | 0.2 | 0.2 | 0.2 |
| 2,4-dimethyl tetrahydro thiophene | 9 | 0.4 | 0.2 | 0.3 | 0.5 |
| The methyl ring is thioether | 13.5 | 1 | 1 | 0.9 | 0.7 |
| Carbon three thiophene | 395 | 13 | 7.9 | 13.2 | 19 |
| Carbon four thiophene | 115 | 13 | 7.4 | 12 | 15.5 |
| Carbon seven thioethers | 15 | 0.6 | 0.2 | 0 | 0.5 |
| Carbon eight thioethers | 12 | 0.9 | 0.5 | 0.5 | 1 |
| Benzothiophene | 40 | 1.8 | 1.2 | 1.4 | 2 |
| The methylbenzene bithiophene | 10 | 0 | 0 | 0.5 | 0.2 |
| The carbon dibenzothiophenes | 13 | 0 | 0 | 0 | 0 |
| Carbon three benzothiophenes | 10 | 0 | 0 | 0 | 0 |
| Add up to | 1844.9 | 318 | 263.1 | 337.1 | 379.4 |
| Desulfurization degree, % | 82.76 | 85.74 | 81.7 | 79.44 |
Table 2
| Gasoline stocks | Embodiment 3 | Embodiment 2 | Embodiment 4 | |
| Desulfurizing agent | APDS-1 | APDS-2 | APDS-3 | |
| Chromatogram sulphur, mg/L | ||||
| Ethanol sulphur | 5 | 6.5 | 6.0 | 6.3 |
| N-propyl mercaptan | 5 | 8.3 | 7.5 | 7 |
| Thiophene | 40.3 | 37.3 | 34.6 | 39.1 |
| N-butyl mercaptan | 5.5 | 2.6 | 2.8 | 4.2 |
| The 2-methylthiophene | 211 | 56 | 55 | 59.6 |
| 3 methyl thiophene | 261 | 49.6 | 47.1 | 51.2 |
| Thiophane | 40.6 | 29.3 | 26 | 34.6 |
| 2-methyl thiophane | 38 | 35.1 | 32.4 | 39 |
| Ethylthiophene | 98 | 47 | 46.5 | 51 |
| 2, the 5-thioxene | 60 | 25.6 | 23 | 17.1 |
| Carbon six mercaptan | 6 | 3 | 2.5 | 2.6 |
| 2, the 4-thioxene | 156 | 18.3 | 15.2 | 18.5 |
| Carbon six thioethers | 11 | 3.9 | 3.5 | 3.7 |
| 2, the 3-thioxene | 218 | 7.9 | 5.3 | 8.9 |
| 3, the 4-thioxene | 52 | 2 | 0.7 | 2.0 |
| 3,3-dimethyl tetrahydro thiophene | 5 | 0.2 | 0.2 | 0.4 |
| 2,4-dimethyl tetrahydro thiophene | 9 | 0.8 | 0.3 | 0.6 |
| The methyl ring is thioether | 13.5 | 1.5 | 0.9 | 0.9 |
| Carbon three thiophene | 395 | 16.4 | 13.2 | 18 |
| Carbon four thiophene | 115 | 15.2 | 12 | 17.8 |
| Carbon seven thioethers | 15 | 0.8 | 0 | 0.9 |
| Carbon eight thioethers | 12 | 1.5 | 0.5 | 2.1 |
| Benzothiophene | 40 | 2.8 | 1.4 | 2.4 |
| The methylbenzene bithiophene | 10 | 0 | 0.5 | 0 |
| The carbon dibenzothiophenes | 13 | 0 | 0 | 0 |
| Carbon three benzothiophenes | 10 | 0 | 0 | 0 |
| Add up to | 1844.9 | 371.6 | 337.1 | 387.9 |
| Desulfurization degree, % | 79.86 | 81.7 | 78.97 |
Claims (13)
1, a kind of desulfurization of hydrocarbon oil agent is characterized in that this desulfurizing agent is made up of the heavy % of rare earth Y type zeolite 15-60 heavy %, inorganic oxide 10-60 heavy %, clay 0-75 that contains through the phosphorus modification that with the catalyst weight is benchmark; The wherein said rare earth Y type zeolite that contains through the phosphorus modification contains with P
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 0.5-8 of meter, with RE
2O
3The rare earth that accounts for the heavy % of this zeolite weight 18-35 of meter, and the silica alumina ratio of this zeolite is less than 6, and described inorganic oxide is selected from amorphous aluminum silicide, aluminium oxide and/or silica.
2,, it is characterized in that described desulfurizing agent is made up of the heavy % of rare earth Y type zeolite 20-55 heavy %, inorganic oxide 10-60 heavy %, clay 0-65 that contains through the phosphorus modification that with the catalyst weight is benchmark according to the desulfurizing agent of claim 1.
3,, it is characterized in that describedly forming by the heavy % of rare earth Y type zeolite 30-50 heavy %, inorganic oxide 10-60 heavy %, clay 5-60 that contains that with the catalyst weight is benchmark through the phosphorus modification according to the desulfurizing agent of claim 2.
4,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification is selected from: the mixture of one or more among REY, REHY, the REUSY according to the desulfurizing agent of claim 1.
5,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification is REY and/or REHY according to the desulfurizing agent of claim 4.
6,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification is REY according to the desulfurizing agent of claim 5.
7, according to the desulfurizing agent of claim 1, the silica alumina ratio that it is characterized in that described zeolite is less than 5.
8,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification contains with RE according to the desulfurizing agent of claim 1
2O
3The rare earth that accounts for the heavy % of this zeolite weight 20-35 of meter.
9,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification contains with RE according to the desulfurizing agent of claim 8
2O
3The rare earth that accounts for the heavy % of this zeolite weight 25-35 of meter.
10,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification contains with P according to the desulfurizing agent of claim 1
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 1-7 of meter.
11,, it is characterized in that the described rare earth Y type zeolite that contains through the phosphorus modification contains with P according to the desulfurizing agent of claim 10
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 2-6 of meter.
12,, it is characterized in that described clay is selected from one or more the mixture in kaolin, halloysite, imvite, bentonite, the sepiolite according to the desulfurizing agent of claim 1.
13,, it is characterized in that described clay is a kaolin according to the desulfurizing agent of claim 1.
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|---|---|---|---|
| CN 03153767 CN1261218C (en) | 2003-08-20 | 2003-08-20 | Hydrocarbon desulfurizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153767 CN1261218C (en) | 2003-08-20 | 2003-08-20 | Hydrocarbon desulfurizer |
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| CN1583966A CN1583966A (en) | 2005-02-23 |
| CN1261218C true CN1261218C (en) | 2006-06-28 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081369B (en) * | 2006-05-31 | 2010-05-12 | 中国石油化工股份有限公司 | Y type zeolites containing rare-earth and high content of silicon and method of making the same |
| CN101134914B (en) * | 2006-08-31 | 2012-02-15 | 中国石油化工股份有限公司 | Catalytic hydroprocessing adsorbing desulfurization for hydrocarbon oil in fixed bed reactor |
| CN101433819B (en) * | 2007-11-15 | 2012-09-12 | 中国石油化工股份有限公司 | Desulphurization sorbent composition |
| CN101434862B (en) * | 2007-11-15 | 2013-06-05 | 中国石油化工股份有限公司 | Method for reducing sulfide in light hydrocarbon oil |
| CN101434854B (en) * | 2007-11-15 | 2013-03-06 | 中国石油化工股份有限公司 | Sorbent for reducing sulfur content of light hydrocarbon oil |
| CN102895946A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof |
| CN104549138B (en) * | 2013-10-28 | 2017-09-15 | 中国石油化工股份有限公司 | Adsorbent of molecular sieve containing Ni and preparation method thereof |
| CN104549140B (en) * | 2013-10-28 | 2017-05-17 | 中国石油化工股份有限公司 | Ion exchange modified molecular sieve adsorbent and preparation method thereof |
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2003
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