CN1958730B - Method for reducing content of sulphur in gasoline - Google Patents

Abstract

This invention discloses a method for lowering sulfur content of gasoline. The method comprises: contacting sulfur-containing crude oil with a desulfurization composition. The desulfurization composition comprises molecular sieves as desulfurization elements. The skeleton of each molecular sieve contains vanadium and a second metallic element M, which is selected from IIA, IIB, IVB, VIIB and VIIIBof the period table of elements or one of lanthanide rare earth elements. The method can effectively lower the sulfur content of gasoline in normal fluid cracking (FCC) condition, and improve the hydrothermal stability of FCC catalyst.

Description

A kind of method that reduces content of sulfur in gasoline

Technical field

The present invention relates to a kind of cracking method of hydrocarbon ils, more particularly, is the method that reduces content of sulfur in gasoline about a kind of catalytic cracking process.

Background technology

Fluid catalytic cracking (FCC) is a kind of oil refining process, and the residual oil that is about to heavy ends such as vacuum distillate or more heavy constituent is converted into the main process of the less cut of molecule, existing large-scale commercial applications in refining of petroleum.Catalytically cracked material contains the sulphur that exists with the organosulfur compound form usually, for example mercaptan, thioether, thiophene and substituted thiophene etc., in cracking process, pass through to decompose non-thiophene sulfide, the sulphur of half can be converted into hydrogen sulfide, therefore very easily there is sulphur impurity in the crackate, they enter in the gasoline fraction with certain proportion, and enter gasoline pool.The distribution of sulphur in crackate is all relevant with stock oil, catalyzer, additive and other certain operations conditions.Because it is to the pay attention to day by day of environment protection, also more and more stricter in recent years at the restriction index of sulfur in gasoline content.Restriction sulfur in gasoline content is not only favourable to environment protection, and also very important for the sulfur poisoning degree that reduces vehicle catalytic converter.

Common desulfurization method is to carry out hydrotreatment removing partial vulcanization compound wherein, thereby reduces the sulphur content in the gasoline.Usually select the FCC raw material is carried out the hydrogenation pre-treatment, perhaps after the FCC process, crackate is carried out hydrotreatment.The former hydrogen-consuming volume is big, and the investment of equipment and running expense are all higher; The latter understands the part alkene in the saturated products, causes the loss of octane value.From the viewpoint of economy, preferably can be in cracking process desulfurization and additional other treating processes.In order to reach this purpose, part Study work concentrates on and remove desulfuration from the flue gas of revivifier, but in fact this method does not have to show effect (the Krishna et.al. that significantly reduces the product sulphur content, Additives Improve FCC Process, Hydrocarbon Processing, 1991,11,59-66); Another part research work then concentrates on the auxiliary agent that has desulfurizing function in the FCC process by interpolation, realizes the direct desulfurization in the FCC process.

To having studies have shown that of desulfurizing function auxiliary agent, some metallic elements such as V, Ni, Cu, Cd, Sn, B, Al, Zn etc. have the function of this respect.For example, Grace Davison company has developed GFS sulfur-lowing catalyst and the GSR sulfur prodegradant that reduces the FCC content of sulfur in gasoline; In US5376608 and US5525210, a kind of cracking catalyst with desulfidation is disclosed, it comprises a kind of zeolite molecular sieve that is scattered on the inorganic oxide carrier, with the alumina material in a kind of load L acid site, the Ni by 1～50%, Cu, Zn, Ag, Cd, In, Sn, Hg, Tl, Pb, Bi, B, Al, element such as Ga or compound loaded formation.In US6482315, disclose a kind of on the non-molecular sieve carrier as alumina material on the sweetening additive of a large amount of vanadium of load (5～10 heavy % vanadium), it is used with the conventional FCC cracking catalyst that contains y-type zeolite can demonstrate the effect that better removes content of sulfur in gasoline.In US2002/0179498A and US2003/0089639A, a kind of catalytic cracking process liquid crackate that is used for reducing is disclosed, the desulfurization catalyst of the sulphur content of pressure gasoline particularly, this catalyzer comprise that a kind of oxidation state that comprises is greater than zero metal component with improve catalyst stability and desulphurizing activated rare earth cerium in Molecular Sieve Pore.Molecular sieve is generally faujusite such as USY, and main desulfurization component is a kind of metal in the 3rd cycle, preferred vanadium.

In CN1261618A and CN1281887A, a kind of desulfurization catalyst composition that is used for reducing catalytic cracking process liquid crackate sulphur content is disclosed, it comprises a kind of porous molecular sieve, this molecular sieve comprises above oxidation state of zeroth order and the metal component in Molecular Sieve Pore and improves the rare earth component of cracking activity. and molecular sieve is large aperture zeolite such as USY or zeolite beta or mesopore zeolite such as ZSM-5, a kind of metal in main 4 cycles of desulfurization component Chang Weidi, preferred vanadium, the rare earth metal preferred cerium.

Because catalyzer do not exist only under the hot conditions of cracking reaction, also will be through the recirculation process of steam stripped and oxidation regeneration, so the stability of catalyzer, particularly hydrothermal stability are very important.But the cracking catalyst with desulfidation above-mentioned is to load on metallic compound and forms on certain carrier, metal ion is on the ion-exchange sites, on hydrothermal stability, have problems, under action of high temperature, the metal of load can be moved on the molecular sieve from original position, not only lose original desulphurizing activatedly, more seriously vanadium can destroy the rock steady structure as active component molecular sieve in the FCC catalyzer, causes whole catalyzer to lose activity at last.

Summary of the invention

The objective of the invention is deficiency, a kind of method with reduction sulfur content of catalytic cracking gasoline of higher desulfuration ability and good hydrothermal stability is provided at the desulfurization cracking catalyst of metallic compound load in the prior art.

Method provided by the invention is included under the conventional catalytic cracking condition, sulphur-bearing crude is contacted with a kind of composition with desulfidation, wherein said composition with desulfidation contain contain the v element and the second metallic element M in a kind of skeleton structure molecular sieve as desulphurizing activated constituent element, the said second metallic element M is selected from a kind of in periodic table of elements IIA, IIB, IVB, VIIB, VIIIB or the lanthanide series rare-earth elements.This method can effectively reduce the content of sulfur in gasoline of FCC process, and improves the hydrothermal stability of FCC catalyzer.

More particularly, composition described in the method provided by the invention with desulfidation, mainly form by cracking activity constituent element, desulphurizing activated constituent element, carrier and binding agent etc., said desulphurizing activated constituent element is the molecular sieve that contains the v element and the second metallic element component in the skeleton structure simultaneously, and molecular sieve content preferably accounts for 1～20 heavy % of catalyzer, more preferably 7～15 weighs %.In addition, the ratio preferred 1～50, more preferably 3～20 that contains the molecular sieve of v element in wherein said cracking activity constituent element and the skeleton structure.

The composition with desulfidation described in the method provided by the invention contains the molecular sieve of the v element and second metal component simultaneously in the wherein said skeleton structure, abbreviate the bimetal molecular sieve as, is meant that the vanadium and second metallic element enter the skeleton of molecular sieve, with V ⁴⁺/ V ⁵⁺And M ^N+Form is combined in the framework of molecular sieve, molecular sieve as backbone element, the vanadium and second metal exist form with FT-IR, ESR, the common sign of NMR and XPS determined (but reference Vanadosilicate catalysts prepared from differentvanadium sources and their characteristics in methanol to conversion (A.Miyamoto, D.Medhanavyn and T.Inui, Applied Catalysis, 28 (1986) 89-103), Synthesis and Characterization of the Vanadium-incorporated MolecularSieve VAPO-5 (S.H.Jhung, Y.S.UH and H.Chon, Applied Catalysis 62 (1990) 61-72) and Synthesis, characterization and catalytic properties ofvanadium silicates with a ZSM-48 structure (A.Tuel and Y.Ben Taarit.Applied Catalysis A:General, 102 (1993) 201-204)).Wherein said second metal is preferably from metals such as Be, Mg, Ti, Mn, Zn, Fe, Co or Ce.

Said bimetal molecular sieve can be the V-Si molecular sieve (as M-VS-1 and M-VS-2) that contains second metal (M), wherein vanadium, second metal and silicon are as backbone element, the mol ratio of silicon and vanadium is preferred 10～100, the mol ratio preferred 10～100 of the silicon and second metal; Can be for containing the phosphoric acid vanadium aluminum molecular screen (M-VAPO-n of second metal, as VAPO-5, VAPO-11, VAPO-31, VAPO-17 etc.), wherein vanadium, aluminium, phosphorus and second metal are as backbone element, equally, the aluminium wherein and the mol ratio of vanadium are preferred 10～100, the mol ratio preferred 10～100 of the aluminium and second metal; Also can be for containing the phosphoric acid vanadium sial of second metal, the ratio of silicon and aluminium is arbitrarily, at this moment sial is simultaneously as backbone element, recently characterize the content of vanadium in the skeleton with silicon vanadium mole. no matter contain the phosphoric acid vanadium aluminium or the phosphoric acid silicon vanadium aluminum molecular screen of second metal, phosphorus element content does not have obvious influence to the performance of composition in the skeleton.

Composition described in the method provided by the invention with desulfidation, wherein said cracking activity constituent element is that conventional catalytic cracking catalyst usually adopts, can be various macropores and/or mesoporous molecular sieve, for example Y zeolite and ZSM-5 zeolite etc., they can obtain through modification, the Y zeolite of the containing metal constituent element that obtains as USY, REUSY, REY, REHY or through various metal oxide treated; Said ZSM-5 zeolite can be for rare earth modified or through the ZSM-5 zeolite of rare earth and phosphorus modification (brief note is ZRP, as putting down in writing among the CN1093101A).

Composition described in the method provided by the invention with desulfidation, wherein said carrier is various clays, as kaolin etc.; Said binding agent can be selected from the mixture of one or both or three in silicon sol, aluminium colloidal sol and the pseudo-boehmite.

Composition described in the method provided by the invention with desulfidation, owing to introduce the molecular sieve that contains the v element and second metallic element in the skeleton with desulfidation, can be used as fluid cracking catalyst uses, under the situation that does not influence conventional FCC operational condition, effectively reduce the content of sulfur in gasoline of FCC process, and improve the hydrothermal stability of catalyzer; Compare with the catalyzer of the used load vanadium of prior art, v element can stably be present in the framework of molecular sieve, avoided because the migration of vanadium to cracking catalyst activity constituent element, as the Y zeolite structural damage; The introducing of second metallic element has not only improved the desulfurization performance of catalyzer, has also strengthened the stability of cracking catalyst, improves product and distributes.

Embodiment

The present invention is further illustrated below in conjunction with embodiment, but not thereby limiting the invention.

Among the embodiment, the elementary composition of said bimetal molecular sieve carries out quantitative analysis with X-ray fluorescence spectra in the catalyzer; Its crystalline phase and degree of crystallinity XRD determining.

Desulphurizing activated constituent element is the VAPO-5 that skeleton contains second metal in the catalyzer of embodiment 1～6.

Embodiment 1

Synthesizing of Ce-VAPO-5 molecular sieve: 15g dry glue powder (Al ₂O ₃Content 65.8%, the Chang Ling catalyst plant is produced), add water 60mL making beating after 60 minutes to wherein slowly dripping 14g ortho-phosphoric acid solution (phosphorus acid content 85%, Beijing chemical reagent work produces).Stir and add 2.3g vanadylic sulfate (V content 22% after 10 minutes earlier, be dissolved in the 2g water), stir after 5 minutes and to add 0.75g Cerium II Chloride (being dissolved in the 2g water), continue under the room temperature to stir that the speed with 1mL/min adds 16ml template triethylamine (content 98%, Beijing chemical reagent work produces) after 60 minutes.Continue to stir after 1 hour, placed 175 ℃ of dynamic crystallizations of crystallizing kettle 72 hours.Behind the products therefrom filtration washing in 80 ℃ of oven dry, sample in flowing air temperature-programmed calcination (120 ℃, 1 hour; 3 ℃/minute are warming up to 550 ℃, keep 4 hours postcooling to room temperature).The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and its aluminium vanadium mol ratio is 25, and aluminium cerium mol ratio is 50.

According to Ce-VAPO-5 10 heavy %, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, the catalyzer of pseudo-boehmite 20 heavy % and kaolin 30 heavy % is formed, above-mentioned synthetic Ce-VAPO-5 and above-mentioned each component are mixed, after adding suitable quantity of water and stirring, the spray-dried catalyst A 1 that is prepared into.

Embodiment 2

Synthesizing of Fe-VAPO-5 molecular sieve: the preparation method wherein replaces Cerium II Chloride with iron nitrate with embodiment 1, is contained the aluminium phosphate molecular sieve of vanadium and iron simultaneously.The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and its aluminium vanadium mol ratio is 20, and the ferro-aluminum mol ratio is 50.

According to the heavy % of Fe-VAPO-510, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, the catalyzer of pseudo-boehmite 20 heavy % and kaolin 30 heavy % is formed the spray-dried catalyst A 2 that is prepared into.

Embodiment 3

Synthesizing of Mg-VAPO-5 molecular sieve: the preparation method wherein replaces Cerium II Chloride with magnesium chloride with embodiment 1, is contained the aluminium phosphate molecular sieve of vanadium and magnesium simultaneously.The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and its aluminium vanadium mol ratio is 25, and the magnalium mol ratio is 25.

According to the heavy % of Mg-VAPO-510, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, the catalyzer of pseudo-boehmite 20 heavy % and kaolin 30 heavy % is formed the spray-dried catalyst A 3 that is prepared into.

Embodiment 4

Synthesizing of Ti-VAPO-5 molecular sieve: the preparation method wherein replaces Cerium II Chloride with titanium sulfate with embodiment 1, is contained the aluminium phosphate molecular sieve of vanadium and titanium simultaneously.The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and its aluminium vanadium mol ratio is 30, and aluminium titanium mol ratio is 30.

According to the heavy % of Ti-VAPO-510, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, the catalyzer of pseudo-boehmite 20 heavy % and kaolin 30 heavy % is formed the spray-dried catalyst A 4 that is prepared into.

Embodiment 5

Synthesizing of Mn-VAPO-5 molecular sieve: the preparation method wherein replaces Cerium II Chloride with Manganous chloride tetrahydrate with embodiment 1, is contained the aluminium phosphate molecular sieve of vanadium and manganese simultaneously.The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and its aluminium vanadium mol ratio is 25, and aluminium manganese mol ratio is 40.

According to the heavy % of Mn-VAPO-510, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, the catalyzer of pseudo-boehmite 20 heavy % and kaolin 30 heavy % is formed the spray-dried catalyst A 5 that is prepared into.

Embodiment 6

Synthesizing of Zn-VAPO-5 molecular sieve: the preparation method wherein replaces Cerium II Chloride with zinc nitrate with embodiment 1, is contained the aluminium phosphate molecular sieve of vanadium and zinc simultaneously.The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and its aluminium vanadium mol ratio is 25, and aluminium zinc mol ratio is 50.

According to Zn-VAPO-5 10 heavy %, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, the catalyzer of pseudo-boehmite 20 heavy % and kaolin 30 heavy % is formed the spray-dried catalyst A 6 that is prepared into.

Comparative Examples 1

Comparative catalyst DB-1 consists of: (lattice constant is the REUSY molecular sieve Content of rare earth 68 heavy %) 40 heavy %, aluminium colloidal sol 10 heavy %, pseudo-boehmite 20 heavy %, kaolin 30 heavy %.

Comparative Examples 2

Comparative catalyst DB-2 consists of: VAPO-5 10 heavy %, (lattice constant is the REUSY molecular sieve

Content of rare earth 68 heavy %) 30 heavy %, aluminium colloidal sol 10 heavy %, pseudo-boehmite 20 heavy %, kaolin 30 heavy %.Wherein the preparation method of VAPO-5 does not just wherein add second metallic element with embodiment 1.

Catalyst A 1～A6 and contrast medium DB-1, the DB-2 of preparation were worn out 8 hours under 800 ℃ of 100% water vapour respectively, carry out the evaluation of cracking reaction.The characteristic parameter that is used for the sulfur-bearing stock oil of cracking reaction sees Table 1.The cracking performance evaluation result sees Table 2.

Table 1

Density (20 ℃), g/cm 3Refractive power (70 ℃) viscosity (50 ℃), mm 2/ s viscosity (100 ℃), mm 2/ s acid number, mgKOH/g zero pour, ℃ aniline point, ℃ carbon residue, m%	0.9154 1.4926 34.14 6.962 0.27 35 82.0 0.18
		Elementary composition C, m% H, m% S, m% N, m%	85.38 12.03 2.0 0.16
Metal content, ppm Ni V Cu Fe Na	＜0.1 ＜0.1 0.1 0.5 0.8
		Four components, m% stable hydrocarbon aromatic hydrocarbons gum asphalt	64.0 32.0 4.0 0.0
Boiling range, ℃ IBP/5% 10%/30% 50%/70% 90%/95%	329/363 378/410 436/462 501/518

Table 2

Catalyzer	DB-1	DB-2	A1	A2	A3	A4	A5	A6
									MA(800℃/8h)	70	70	70	70	70	70	70	70

Catalyzer	DB-1	DB-2	A1	A2	A3	A4	A5	A6
									C/O	1.47	1.47	1.47	1.47	1.47	1.47	1.47	1.47
Temperature of reaction/℃	500	500	500	500	500	500	500	500
									Dry gas	2.14	1.79	1.63	1.78	1.51	1.58	1.85	2.11
Liquefied gas	10.18	10.94	10.21	9.05	9.71	8.31	9.70	10.99
									Gasoline	54.05	50.14	53.32	53.53	52.61	55.46	52.68	52.00
Diesel oil	20.34	22.33	21.39	20.56	21.72	20.71	21.67	21.53
									Heavy oil	10.38	12.00	10.45	12.92	10.93	10.92	11.29	10.63
Coke	2.91	2.80	2.99	2.16	3.52	3.02	2.80	2.74
									Amount to	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0
Transformation efficiency/m%	69.28	65.67	68.16	66.52	67.34	68.37	67.04	67.84
									Yield of light oil/m%	74.39	72.47	74.71	74.10	74.34	76.17	74.36	73.53
Light receipts+liquefied gas/m%	84.57	83.40	84.92	83.14	84.04	84.48	84.06	84.52
									Heavy oil/coke	3.56	4.28	3.50	5.99	3.11	3.61	4.03	3.88
Coke/transformation efficiency	0.04	0.04	0.04	0.03	0.05	0.04	0.04	0.04
									Content of sulfur in gasoline, mg/L	420.93	290.18	241.54	247.89	262.37	268.70	267.77	253.41
Desulfurization degree %	base	31.1	42.6	41.1	37.7	36.2	36.4	39.8

As can be seen from Table 2, catalyst A 1～A6 compares with the comparative catalyst DB-1 that does not add the bimetal molecular sieve, and the sulphur content of gasoline reduces greatly, and desulfurization degree is all above more than 35%; Compare with only having added the comparative catalyst DB-2 that contains vanadium molecular sieve VAPO-5, transformation efficiency increases, and the sulphur content of gasoline be than can further reducing, and sweetening effectiveness is more remarkable.

Embodiment 7

Be that with catalyst A 1 difference of embodiment the REUSY molecular sieve among the A1 substitutes with the rare earth USY molecular sieve of ZnO modification, this molecular sieve is labeled as ZARY, and wherein ZnO content 6 weighs %, and content of rare earth is 10 heavy %, and USY content is 84 heavy %, catalyzer numbering A1 '.

Comparative Examples 3

Comparative catalyst DB-3 consists of: ZARY molecular sieve 40 heavy %, aluminium colloidal sol 10 heavy %, pseudo-boehmite 20 heavy %, kaolin 30 heavy %.Evaluation result sees Table 3.

Comparative Examples 4

Comparative catalyst DB-4 consists of: the heavy % of VAPO-510, ZARY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, pseudo-boehmite 20 heavy %, kaolin 30 heavy %.Evaluation result sees Table 3.

Table 3

Catalyzer	DB-3	DB-4	Catalyst A 1 '
				MA(800℃/8h)	70	70	70
C/O	1.47	1.47	1.47
				Temperature of reaction/℃	500	500	500
Dry gas	2.01	1.87	1.66
				Liquefied gas	10.62	11.23	10.30
Gasoline	53.18	50.36	52.57
				Diesel oil	20.65	22.05	21.49
Heavy oil	11.02	12.11	11.13
				Coke	2.52	2.38	2.85
Amount to	100.0	100.0	100.0
				Transformation efficiency/m%	68.33	65.84	67.38
Yield of light oil/m%	73.83	72.41	74.06

Catalyzer	DB-3	DB-4	Catalyst A 1 '
				Light receipts+liquefied gas/m%	84.45	83.64	84.36
Heavy oil/coke	4.37	5.09	3.91
				Coke/transformation efficiency	0.04	0.04	0.04
Content of sulfur in gasoline, mg/L	431.45	297.21	250.68
				Desulfurization degree %	base	31.1	41.9

Embodiment 8

The desulfurization component is synthetic Fe-VAPO-5 among the embodiment 2, accounts for 13 heavy %, and USY accounts for 35 heavy %, and (ZRP is phosphorus and rare earth modified ZSM-5 molecular sieve to the heavy % of ZRP10, and the industrial trade mark is ZRP-7, and the Qilu Petrochemical catalyst plant is produced, SiO ₂/ Al ₂O ₃Be 80), aluminium colloidal sol 10 heavy %, pseudo-boehmite 16 heavy %, kaolin 16 heavy %.Catalyzer numbering A2 '.Evaluation result sees Table 4.

Comparative Examples 5

Comparative catalyst DB-5 consists of, USY molecular sieve 48 heavy %, the heavy % of ZRP10, aluminium colloidal sol 10 heavy %, pseudo-boehmite 16 heavy %, kaolin 16 heavy %.Evaluation result sees Table 4.

Comparative Examples 6

Comparative catalyst DB-6 consists of, the heavy % of VAPO-513, USY molecular sieve 35 heavy %, the heavy % of ZRP10, aluminium colloidal sol 10 heavy %, pseudo-boehmite 16 heavy %, kaolin 16 heavy %.Evaluation result sees Table 4.

Table 4

Catalyzer	DB-5	DB-6	Catalyst A 2 '
				MA(800℃/8h)	70	70	70
C/O	1.47	1.47	1.47
				Temperature of reaction/℃	500	500	500
Dry gas	1.95	1.90	1.91
				Liquefied gas	11.68	10.12	10.60
Gasoline	52.26	52.14	52.09

Catalyzer	DB-5	DB-6	Catalyst A 2 '
				Diesel oil	20.07	20.76	20.77
Heavy oil	11.33	12.87	12.68
				Coke	2.71	2.21	1.95
Amount to	100.0	100.0	100.0
				Transformation efficiency/m%	68.60	66.37	66.55
Yield of light oil/m%	72.33	72.90	72.86
				Light receipts+liquefied gas/m%	84.01	83.02	83.46
Heavy oil/coke	4.18	5.82	6.50
				Coke/transformation efficiency	0.04	0.03	0.03
Content of sulfur in gasoline, mg/L	418.34	293.12	256.31
				Desulfurization degree %	base	29.9	38.7

Embodiment 9～11

The catalyzer of embodiment 9～11 is designated as A7, A8 and A9 respectively, the REUSY molecular sieve content is 35 weight %, pseudo-boehmite 20 heavy %, kaolin content is 30 weight %, difference is that Al/V among the used Ce-VAPO-5 (mol) is 25, Al/Ce (mol) is respectively 120,70 and 20, and content is respectively 8 heavy %, 5 heavy % and 2 heavy %, and the aluminium sol content is respectively 7 heavy %, 10 heavy % and 13 heavy %.Evaluation result sees Table 5, lists file names with the evaluation result of comparative catalyst DB-1 and DB-2 in the table 5.

Table 5

Catalyzer	DB-1	DB-2	A7	A8	A9
						Al/Ce(mol)			120	70	20
MA(800℃/8h)	70	70	70	70	70
						C/O	1.47	1.47	1.47	1.47	1.47
Temperature of reaction/℃	500	500	500	500	500

Catalyzer	DB-1	DB-2	A7	A8	A9
						Dry gas	2.14	1.79	2.09	1.87	2.01
Liquefied gas	10.18	10.94	10.16	10.21	10.45
						Gasoline	54.05	50.14	53.18	53.44	53.38
Diesel oil	20.34	22.33	21.71	21.39	20.72
						Heavy oil	10.38	12.00	10.78	10.85	11.23
Coke	2.91	2.80	2.08	2.24	2.21
						Amount to	100.0	100.0	100.0	100.0	100.0
Transformation efficiency/m%	69.28	65.67	67.51	67.76	68.05
						Yield of light oil/m%	74.39	72.47	74.89	74.83	74.10
Light receipts+liquefied gas/m%	84.57	83.40	85.05	85.04	84.55
						Heavy oil/coke	3.56	4.28	5.18	4.84	5.08
Coke/transformation efficiency	0.04	0.04	0.03	0.03	0.03
						Content of sulfur in gasoline, mg/L	420.93	290.18	260.21	254.50	261.60
Desulfurization degree %	base	31.1	38.2	39.5	37.8

By table 5 as seen, contain in the vanadium molecular sieve at desulphurizing activated constituent element and to introduce second metal component and can further improve the desulphurizing activated of catalyzer, the difference of the second metal component introducing amount then causes different desulfurization results.

Desulphurizing activated constituent element is the VAPO-11 that skeleton contains second metal in the catalyzer of embodiment 12～15.

Embodiment 12

Mg-VAPO-11's is synthetic: 15g dry glue powder (Al ₂O ₃Content 65.8%, the Chang Ling catalyst plant is produced), add water 60mL making beating after 60 minutes to wherein slowly dripping 14g ortho-phosphoric acid solution (phosphorus acid content 85%, Beijing chemical reagent work produces). stir adding 2.3g five water vanadylic sulfate (V content 22% after 10 minutes, be dissolved in the 2g water), stir and add quantitative magnesium chloride solution after 5 minutes, continue to stir under the room temperature that the speed with 1mL/min adds 13.6mL template dipropyl amine (content 98% after 60 minutes, Beijing chemical reagent work produces). continue to stir after 1 hour, placing 200 ℃ of dynamic crystallizations of crystallizing kettle 96 hours. the X-ray diffraction of products therefrom (XRD) spectrogram has the feature of VAPO-11 molecular sieve, aluminium vanadium mol ratio is 25, and the magnalium mol ratio is 25.

To synthetic Mg-VAPO-11 as stated above, add the REUSY molecular sieve, aluminium colloidal sol, pseudo-boehmite and kaolin prepare catalyzer with embodiment 1 method, wherein the content of Mg-VAPO-11 is 10 heavy %, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, pseudo-boehmite 20 heavy % and kaolin 30 heavy %, the spray-dried catalyzer that is prepared into is numbered A10.Evaluation result sees Table 6.

Embodiment 13～15

The catalyzer of embodiment 13～15 is designated as A11 respectively, A12 and A13.

Compare with catalyst A 10, difference is that the magnalium mol ratio is respectively 130,75 and 15 among the used Mg-VAPO-11, and content is respectively 12 heavy %, 6 heavy % and 3 heavy %, and kaolin 28 heavy %, the aluminium sol content is respectively 5 heavy %, 11 heavy % and 13 heavy %.Evaluation result sees Table 6.

Comparative Examples 7

Comparative catalyst DB-7 consists of: the heavy % of VAPO-1110, REUSY molecular sieve 30 heavy %, aluminium colloidal sol 10 heavy %, pseudo-boehmite 20 heavy %, kaolin 30 heavy %.Wherein the preparation method of VAPO-11 does not just wherein add second metallic element with embodiment 12.Evaluation result sees Table 6.

Evaluation result table 6 lists file names with the cracking result of Comparative Examples DB-1 in the table 6.

Table 6

Catalyzer	DB-1	DB-7	A10	A11	A12	A13
							Al/Mg(mol)			25	130	75	15
MA(800℃/8h)	70	70	70	70	70	70
							C/O	1.47	1.47	1.47	1.47	1.47	1.47
Temperature of reaction/℃	500	500	500	500	500	500
							Dry gas	2.14	1.94	2.04	1.87	1.98	2.12
Liquefied gas	10.18	10.87	9.97	10.11	10.69	10.03
							Gasoline	54.05	50.97	52.10	52.14	52.07	52.32
Diesel oil	20.34	21.65	21.95	21.58	21.56	21.87
							Heavy oil	10.38	11.82	10.89	11.01	10.74	10.93
Coke	2.91	2.75	3.05	3.29	2.96	2.73

Catalyzer	DB-1	DB-7	A10	A11	A12	A13
							Amount to	100.0	100.0	100.0	100.0	100.0	100.0
Transformation efficiency/m%	69.28	66.53	67.16	67.41	67.70	67.20
							Yield of light oil/m%	74.39	72.62	74.05	73.72	73.63	74.19
Light receipts+liquefied gas/m%	84.57	83.49	84.02	83.83	84.32	84.22
							Heavy oil/coke	3.56	4.29	3.57	3.35	3.63	4.00
Coke/transformation efficiency	0.04	0.04	0.04	0.05	0.04	0.04
							Content of sulfur in gasoline, mg/L	420.93	300.14	269.52	266.70	258.60	284.31
Desulfurization degree %	base	28.7	36.0	36.6	38.5	32.4

As can be seen from Table 6, A10～A13 compares with not adding the catalyzer DB-1 that contains the vanadium molecular sieve, and the sulphur content of gasoline reduces greatly, and desulfurization degree is all above more than 30%; Compare with only having added the comparative catalyst DB-7 that contains vanadium molecular sieve VAPO-11, transformation efficiency increases, and the sulphur content of gasoline be than can further reducing, and sweetening effectiveness strengthens to some extent.

Claims (17)

1. method that reduces content of sulfur in gasoline, be included under the conventional catalytic cracking condition, sulphur-bearing crude is contacted with a kind of composition with desulfidation, wherein said composition with desulfidation contain contain the v element and the second metallic element M in a kind of skeleton structure molecular sieve as desulphurizing activated constituent element, the said second metallic element M is selected from a kind of in periodic table of elements IIA, IIB, IVB, VIIB, VIIIB or the lanthanide series rare-earth elements.

2. according to the method for claim 1, have that the said second metallic element M is selected from Be, Mg, Ti, Mn, Zn, Fe, Co or Ce in the composition of desulfidation.

3. according to the method for claim 1, the composition with desulfidation mainly is made up of the molecular sieve that contains the v element and the second metallic element M in carrier, binding agent, macropore and/or mesoporous molecular sieve and the skeleton structure.

4. according to the method for claim 1 or 3, the molecular sieve that contains the v element and the second metallic element M in the said skeleton structure accounts for 1～20 heavy %.

5. according to the method for claim 4, the molecular sieve that contains the v element and the second metallic element M in the said skeleton structure accounts for 7～15 heavy %.

6. according to the method for claim 3, the ratio that contains the molecular sieve of the v element and the second metallic element M in said macropore and/or mesoporous molecular sieve and the skeleton structure is 1～50.

7. according to the method for claim 6, the ratio that contains the molecular sieve of the v element and the second metallic element M in said macropore and/or mesoporous molecular sieve and the skeleton structure is 3～20.

8. according to the method for claim 1, one or more the mixture of the molecular screening that contains the v element and the second metallic element M in the said skeleton structure in vanadium metal si molecular sieves, metal tripolyphosphate vanadium aluminum molecular screen and metal tripolyphosphate vanadium Si-Al molecular sieve.

9. according to the method for claim 8, the mol ratio of aluminium and vanadium is 10～300 in the said metal tripolyphosphate vanadium aluminum molecular screen.

10. according to the method for claim 3, wherein said macropore and/or mesoporous molecular sieve are Y zeolite and/or ZSM-5 zeolite.

11. according to the method for claim 10, wherein said Y molecular sieve is super steady Y or hyperastable Y-type RE.

12. according to the method for claim 11, wherein said Y zeolite is through metal oxide modified.

13. according to the method for claim 12, wherein said metal oxide is a zinc oxide.

14. according to the method for claim 10, wherein said ZSM-5 zeolite is through rare earth modified.

15. according to the method for claim 10, wherein said ZSM-5 zeolite is through phosphorus and rare earth modified.

16. according to the method for claim 3, said carrier is a kaolin.

17. according to the method for claim 3, said binding agent is selected from the mixture of one or both or three in silicon sol, aluminium colloidal sol and the pseudo-boehmite.