CN1556175A - Preparation metod of fluidized desulfur catalyst - Google Patents
Preparation metod of fluidized desulfur catalyst Download PDFInfo
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- CN1556175A CN1556175A CNA200310125412XA CN200310125412A CN1556175A CN 1556175 A CN1556175 A CN 1556175A CN A200310125412X A CNA200310125412X A CN A200310125412XA CN 200310125412 A CN200310125412 A CN 200310125412A CN 1556175 A CN1556175 A CN 1556175A
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Abstract
A catalyst for fludized desulfurizing is prepared through preparing clay slurry, adding Al source, Re, Fe, salt and Ti colloid, crystallizing at 120-250 deg.C for 10-48 hr, adding assistant and adhesive, spray drying and calcining in steam at 350-600 deg.C for 0.5-5 hr. Its advantages are high desulfurizing efficience and resistance to metal pollution, and good activity and stability.
Description
Technical field the present invention relates to a kind of preparation method of novel fluidisation desulfurization catalyst, and it belongs to the preparation method of catalytic cracking and desulfurizing catalyst in the petroleum refining process.
90% (quality percentage composition in the present gasoline of background technology, the diesel oil, down together) above sulphur content is come the catalytic cracking component, along with the raising of raw material degree of heaviness, sulphur content becomes the key that reduces gasoline, diesel oil sulphur content in the reduction catalytic cracking component.It is higher that but the cost of sulphur falls in the employing hydrogenation, gasoline component can reduce octane value because of alkene is saturated, the hydrogenation ability of China's refinery is generally lower simultaneously, make most cracked product directly use without hydrotreatment, part sulphur content even up to 1500ppm has produced very big destruction to environment.For the standard of the 800ppm sulphur content that reaches the existing gasoline of country with satisfy the lower sulphur standard of following content, and don't want the hydrogenation means that adopt cost too high just to need a kind of new sulfur method of exploitation.Directly in catalytic cracking process, add the method that desulfurization catalyst reduces the sulphur content of gasoline and diesel product, both can utilize existing catalyzer to add equipment, reduce investment without new device, can regulate the inlet amount of desulfurization catalyst again according to the composition of raw material at any time, be a kind of simple and effective the sulphur method falls.
The fluidisation desulfurization catalyst was succeeded in developing after 1998 abroad, (USP 5525210 for Wormsbecher and Kim, USP5376608) Fa Ming catalytically cracked gasoline sweetening additive can add in the catalytic cracking reaction process at any time, also can be prepared in the catalytic cracking catalyst, play the effect of desulfurization, but the desulfurization degree is limited, adds sweetening additive and can only make the sulphur content in the catalytically cracked gasoline reduce less than 30%.The S Zorb sweetening agent (USP 5710089, and USP 6184176) of Philps Petroleum Company (Phillips Petroleum Company) exploitation in 1999 is a kind of with ZnO/SiO
2-Al
2O
3Be ZnO-Co/SiO
2-Al
2O
3Main composition, in this sweetening agent, adopt the element Zn that sulphur is had selective adsorption, with the sulfur component fractionation by adsorption in the oil product, finish regeneration by the circulation of burning of sweetening agent then.ZnO has the selection adsorption to mercaptan in the sulfide in this auxiliary agent, and is not strong to the thiophene adsorptive power, and thiophene substantially not open loop transform, and sulfur in gasoline alcohol, thioether only account for about 15～25% of total sulfur, so it is not high totally to fall the sulphur amplitude.Therefore, in order to satisfy the more requirement of low sulfur content of oil fuel, develop a kind of cheaply, easy to use, the desulfurization catalyst of excellent performance has important meaning.
Summary of the invention purpose of the present invention just is to prepare a kind of fluidisation desulfurization catalyst that can directly reduce gasoline, diesel oil sulphur content in catalytic cracking process.
The present invention is directed to the deficiencies in the prior art, utilize the crystallization method rare earth element of active element iron and titanium and strong hydrogen transfer activity to be incorporated in the clay composition of heat-resistant antifriction and make a kind of high-efficiency desulfurization catalyzer, directly the ring-type thiophene that content in the raw material is higher is condensed into coke in catalytic cracking process, and utilizes the active rare-earth component with hydrogen transference ability that sulphur is changed into hydrogen sulfide to be removed.This catalyzer not only can strengthen sulfide absorption greatly, and possesses the catalytic activity that sulphur transforms, and improves desulfuration efficiency, reduces the organosulfur in pressure gasoline, the diesel product, as the content of thiophene, thionaphthene, dialkyl benzene thiophthene etc.
In order to realize above-mentioned purpose of the present invention, the preparation method who the invention provides desulfurization catalyst is made up of the following step:
With the clay pulp, add aluminium source, rare earth, molysite, titanium glue, 120～250 ℃ of following crystallization 10～48 hours, add auxiliary agent, the spray-dried moulding of caking agent again, at 350～600 ℃, roasting made catalyzer after 0.5～5.0 hour under 1～100% water vapour, this catalyzer medium clay soil: Al
2O
3: Fe
2O
3: TiO
2: rare earth: R
2O: P
2O
5Mol ratio is 1.2～20: 1: 0.01～0.8: 0.01～0.5: 0.01～0.5: 0.03～0.3: 0.01～0.1, and made catalyst fluidization desulfuration efficiency height, activity stability is good, and anti-metallic pollution ability is strong.
The described clay of method provided by the present invention is for being selected from kaolin, halloysite, one or more in the polynite.
The described aluminium of method provided by the present invention source is a pseudo-boehmite.
The described rare earth of method provided by the present invention is to be selected from solubility La salt, Ce salt, Pr salt, Nd salt and the Sm salt one or more.
The described molysite of method provided by the present invention is for being selected from FeCl
3, Fe (NO
3)
3, ironic oxalate, iron acetate, FeCl
2In one or more.
The described titanium glue of method provided by the present invention is for being selected from TiCl
4, Ti (SO
4)
2, TiOCl
2With general formula be Ti (OR
4)
4Organic titanate in one or more hydrating solution, wherein R
4Be in the alkyl with 2～4 carbon atoms one or more.
The described auxiliary agent of method provided by the present invention is for being selected from trisodium phosphate, potassium pyrophosphate, tripoly phosphate sodium STPP, Potassium tripolyphosphate, the tripolyphosphate ammonium, Trisodium trimetaphosphate, Sodium hexametaphosphate 99, three potassium metaphosphates, one or more in the hexa metaphosphoric acid potassium, wherein the tripolyphosphate ammonium can not use separately.
The described caking agent of method provided by the present invention is for being selected from silica-alumina gel, silicon sol, aluminium colloidal sol, one or more in sial complex sol and the pseudo-boehmite.
The described R of method provided by the present invention
2O is a kind of in potassium oxide and the sodium oxide or their mixture.
The described catalyzer of method provided by the present invention is used for the fluid catalytic cracking process desulfurization.
Compared with prior art, the present invention is a raw material with the clay of cheapness, and titanium, iron, rare earth are incorporated in the catalyst structure, improves desulphurizing activated (embodiment 5) of product greatly.
Description of drawings Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained catalyst sample.
Embodiment following examples will the invention will be further described, but do not limit application of the present invention.
In each of the embodiments described below, used kaolin is the S-1 type kaolin of China Kaolin Co., Ltd, and pseudo-boehmite is produced for research institute of Shandong Aluminium Industrial Corp, and rare-earth salts is produced for Inner Mongol Rare Earth Company, and all the other reagent are commercially available chemically pure reagent.
The kaolin specification: fineness is higher than 350 orders, aluminum oxide 37%, and silicon oxide 48%, ferric oxide 0.6%, purity is greater than 95%;
Pseudo-boehmite specification: specific surface 243m
2/ g, pore volume 0.7ml/g, silicon oxide 0.12%, igloss 20.12%;
Sulfur content in oil products adopts Ignition Lamp Method (GB/T 380) to measure.
Embodiment 1
Get 4.5 moles of kaolin (butt), 0.02 mole of pseudo-boehmite (butt), the cerous nitrate, 0.02 mole in the iron(ic) chloride that add 14 kg-moles deionized waters and 2.0 moles, and mix with the hydrolyzed solution of 0.05 mole of butyl (tetra) titanate, 150 ℃ of following crystallization 36 hours, add 0.08 mole Sodium hexametaphosphate 99 and 0.15 mole aluminium colloidal sol (in aluminum oxide) again, through 420 ℃ of spray drying formings, at 450 ℃, roasting made catalyzer after 3.0 hours under 10% water vapour, it is numbered T-1, and its XRD crystalline phase figure as shown in Figure 1.
Embodiment 2
Get 4.5 moles of kaolin (butt), 0.03 mole of pseudo-boehmite (butt), the lanthanum nitrate, 0.12 mole in the iron(ic) chloride that add 12 kg-moles deionized waters and 1.8 moles, and mix with the making beating of the hydrolyzed solution of 0.08 mole of butyl (tetra) titanate, 130 ℃ of following crystallization 48 hours, add 0.04 mole hexa metaphosphoric acid potassium and 0.20 mole silicon sol (in silicon oxide) again, through the 400 ℃ of drying and mouldings of spraying, at 500 ℃, roasting made catalyzer after 4.0 hours under 20% water vapour, it is numbered T-2, and its XRD crystalline phase figure as shown in Figure 1.
Embodiment 3
Get 3.5 moles of kaolin (butt), 0.01 mole of pseudo-boehmite (butt), the cerous nitrate, 0.04 mole in the iron(ic) chloride that add 9.5 kilograms of deionized waters and 1.2 moles, and mix with the making beating of the hydrolyzed solution of 0.02 mole of butyl (tetra) titanate, 200 ℃ of following crystallization 18 hours, add 0.02 mole trisodium phosphate and 0.17 mole aluminium colloidal sol (in aluminum oxide) again, through the 370 ℃ of drying and mouldings of spraying, at 480 ℃, roasting made catalyzer after 5.0 hours under 100% water vapour, it is numbered T-3, and its XRD crystalline phase figure as shown in Figure 1.
Embodiment 4
Get 4 moles of kaolin (butt), 0.04 mole of pseudo-boehmite (butt), the cerous nitrate, 0.01 mole in the iron(ic) chloride that add 9.0 kilograms of deionized waters and 1.2 moles, and mix with the making beating of the hydrolyzed solution of 0.03 mole of butyl (tetra) titanate, 200 ℃ of following crystallization 18 hours, add 0.02 mole trisodium phosphate and 0.17 mole aluminium colloidal sol (in aluminum oxide) again, through 350 ℃ of spray drying formings, at 550 ℃, roasting made catalyzer after 4.0 hours under 80% water vapour, it is numbered T-4, and its XRD crystalline phase figure as shown in Figure 1.
Comparative Examples
With 300 gram NaY (butt), add 2.1 kilograms of deionized waters, making beating, add 120 gram ammonium chlorides again, 400 gram ammonium phosphate and 45 milliliters of re chlorides (contain rare earth oxide 200g/L, Gansu lanthanide group company), mixes, with the hydrochloric acid adjusting slurry pH value to 3.5 of 2 mol, heat up, reacted 40 minutes down at 90 ℃, filter, washing, filter cake is at 600～620 ℃, roasting is 2.5 hours under 100% water vapour, adding 1.5 liters of deionized waters and 400 milliliters of ammonium phosphate after the roasting in the molecular sieve, mix, is 3.5 with the hydrochloric acid of the 2 mol pH that sizes mixing again, be warmed up to 40 minutes after-filtration of 90 ℃ of reactions, washing, drying obtains comparative catalyst DB-1.
Embodiment 5
The catalyzer that with particle diameter is 40～120 microns was under 800 ℃ in 100% water vapour aging 10 hours, it is desulphurizing activated to estimate it on the small fixed flowing bed reactor, estimating used stock oil is 70% wide fraction and 30% vacuum residuum (sulphur content is 0.517%), 500 ℃ of temperature of reaction, 650 ℃ of regeneration temperatures, catalystoil ratio are 3.5, and the catalyzer Intake Quantity is 150 grams, oil inlet quantity is 40 grams, and air speed is 16h
-1, the addition of desulfurization catalyst accounts for 10%, and all the other are comparative catalyst DB-1.Reaction result sees Table 1.
Embodiment 6
5.74 gram ammonium meta-vanadates are dissolved in and are made into 500 milliliters of solution that contain vanadium 0.4% in 3% aqueous hydrogen peroxide solution, with reference to method (Ind.Eng.Chem.Prod.Dev.1980, the 19th volume of Mitchell, 209 pages) respectively to catalyzer T-1, T-2, T-3, T-4 carries out pollution of vanadium.Catalyzer in 540 ℃ of roastings 1.5 hours, at room temperature soaked 16 hours with an amount of above-mentioned vanadium solution with catalyzer in elder generation, and drying is 24 hours under 120 ℃, 540 ℃ of dryings 4 hours, measure catalyzer T-1, T-2 with the method for embodiment 5 respectively more then, T-3, the desulfurization performance of T-4 the results are shown in Table 1.
Table 1
| Content of sulfur in gasoline/ppm | Gasoline sulfur decreasing ratio/% | Diesel oil sulphur content/ppm | Diesel oil sulfur removal rate/% | ||
| ?????DB-1 | ????1260 | ????0 | ????4310 | ????0 | |
| ??T-1 | Fresh | ????740 | ????41.5 | ????2710 | ????37.2 |
| V pollutes | ????830 | ????33.9 | ????2960 | ????31.4 | |
| ??T-2 | Fresh | ????790 | ????37.5 | ????2490 | ????42.3 |
| V pollutes | ????880 | ????29.6 | ????2940 | ????31.7 | |
| ??T-3 | Fresh | ????680 | ????45.7 | ????2620 | ????39.1 |
| V pollutes | ????740 | ????41.6 | ????3000 | ????30.3 | |
| ??T-4 | Fresh | ????820 | ????35.2 | ????2440 | ????43.4 |
| V pollutes | ????910 | ????27.3 | ????2750 | ????36.2 | |
Annotate: numeral is mass content in the table;
V pollutes and refers to the pollution of catalyzer through vanadium solution;
Gasoline (diesel oil) sulfur removal rate=(Comparative Examples gasoline (diesel oil) sulphur content-gasoline (diesel oil) sulphur content)/Comparative Examples gasoline (diesel oil) sulphur content
From The above results as can be seen, compare with comparative catalyst DB-1, the catalyzer of the present invention's preparation can reduce by 25～45% with the sulphur content in catalytically cracked gasoline and the diesel oil, has the ability of higher desulphurizing activated and preventing from heavy metal pollution.
Claims (10)
1. the preparation method of a fluidisation desulfurization catalyst, with the clay pulp, add aluminium source, rare earth, molysite, titanium glue, 120～250 ℃ of following crystallization 10～48 hours, add auxiliary agent, the spray-dried moulding of caking agent again, at 350～600 ℃, roasting made catalyzer after 0.5～5.0 hour under 1～100% water vapour, this catalyzer medium clay soil: Al
2O
3: Fe
2O
3: TiO
2: rare earth: R
2O: P
2O
5Mol ratio is 1.2～20: 1: 0.01～0.8: 0.01～0.5: 0.01～0.5: 0.03～0.3: 0.01～0.1, and made catalyst fluidization desulfuration efficiency height, activity stability is good, and anti-metallic pollution ability is strong.
2. clay according to claim 1 is for being selected from kaolin, halloysite, one or more in the polynite.
3. aluminium according to claim 1 source is a pseudo-boehmite.
4. rare earth according to claim 1 is to be selected from solubility La salt, Ce salt, Pr salt, Nd salt and the Sm salt one or more.
5. molysite according to claim 1 is for being selected from FeCl
3, Fe (NO
3)
3, ironic oxalate, iron acetate, FeCl
2In one or more.
6. titanium glue according to claim 1 is for being selected from TiCl
4, Ti (SO
4)
2, TiOCl
2With general formula be Ti (OR
4)
4One or more hydrating solution of organic titanate, R wherein
4Be in the alkyl with 2～4 carbon atoms one or more.
7. auxiliary agent according to claim 1 is for being selected from trisodium phosphate, potassium pyrophosphate, tripoly phosphate sodium STPP, Potassium tripolyphosphate, the tripolyphosphate ammonium, Trisodium trimetaphosphate, Sodium hexametaphosphate 99, three potassium metaphosphates, one or more in the hexa metaphosphoric acid potassium, wherein the tripolyphosphate ammonium can not use separately.
8. caking agent according to claim 1 is for being selected from silica-alumina gel, silicon sol, aluminium colloidal sol, one or more in sial complex sol and the pseudo-boehmite.
9. R according to claim 1
2O is a kind of in potassium oxide and the sodium oxide or their mixture.
10. catalyzer according to claim 1 is used for the fluid catalytic cracking process desulfurization.
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|---|---|---|---|
| CNA200310125412XA CN1556175A (en) | 2003-12-31 | 2003-12-31 | Preparation metod of fluidized desulfur catalyst |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767029B (en) * | 2008-12-31 | 2012-06-27 | 中国石油化工股份有限公司 | Heavy oil cracking catalyst and application thereof |
| CN101773845B (en) * | 2009-01-08 | 2012-08-01 | 中国石油化工股份有限公司 | Heavy-oil cracking catalyst and preparation and application method thereof |
| CN101934216B (en) * | 2009-06-30 | 2013-03-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
| CN101934218B (en) * | 2009-06-30 | 2013-03-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
| CN101618314B (en) * | 2008-05-20 | 2013-03-06 | 中国石油化工股份有限公司 | Desulfurizing adsorbent, preparation method and application thereof |
| CN101934217B (en) * | 2009-06-30 | 2013-09-04 | 中国石油化工股份有限公司 | Desulfurization absorbent, and preparation method and application thereof |
-
2003
- 2003-12-31 CN CNA200310125412XA patent/CN1556175A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618314B (en) * | 2008-05-20 | 2013-03-06 | 中国石油化工股份有限公司 | Desulfurizing adsorbent, preparation method and application thereof |
| CN101767029B (en) * | 2008-12-31 | 2012-06-27 | 中国石油化工股份有限公司 | Heavy oil cracking catalyst and application thereof |
| CN101773845B (en) * | 2009-01-08 | 2012-08-01 | 中国石油化工股份有限公司 | Heavy-oil cracking catalyst and preparation and application method thereof |
| CN101934216B (en) * | 2009-06-30 | 2013-03-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
| CN101934218B (en) * | 2009-06-30 | 2013-03-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
| CN101934217B (en) * | 2009-06-30 | 2013-09-04 | 中国石油化工股份有限公司 | Desulfurization absorbent, and preparation method and application thereof |
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