CN102078821B - Cracking catalyst containing mesoporous silica-alumina materials - Google Patents
Cracking catalyst containing mesoporous silica-alumina materials Download PDFInfo
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Abstract
The invention discloses a cracking catalyst containing mesoporous silica-alumina material, wherein the cracking catalyst is composed of cracking active components: clay, adhesive and mesoporous silica-alumina material. The mesoporous silica-alumina material is of a pseudo-boehmite crystal phase structure. In case of the weight of oxide, the anhydrous chemical expression formula is: (0-0.3) Na2O (40-90) Al2O3 (10-60) SiO2, the specific surface area is 200-400m<2>/g, pore volume is 0.5-2.0ml/g, the average pore size is 8-20nm, and the most probable pore size is 5-15nm. The adhesive is selected from one or two mixtures of silica sol or aluminum sol. Compared with the conventional catalyst with pseudo-boehmite, the cracking catalyst has the advantages of low production cost and better crude oil conversion capacity.
Description
Technical field
The present invention relates to a kind of catalyst for cracking heavy oil, specifically about the fluidized catalytic cracking catalyst of a kind of low cost, high heavy oil conversion performance.
Background technology
Catalytic cracking is a kind of oil refining process, be widely used in PETROLEUM PROCESSING industry, as most important process in the crude oil secondary operations, this technique is the main means of production of liquefied petroleum gas, gasoline, kerosene and diesel oil, occupies very important status in oil plant.In catalytic cracking and hydrocracking process, heavy end such as vacuum distillate or more the residual oil of heavy constituent react under catalyst exists, be converted into gasoline, distillate and other liquid cracked product and the lighter following gaseous state cracked product of four carbon, usually need to use the catalysis material with high cracking activity in these courses of reaction.
The micro-pore zeolite catalysis material is widely used in petroleum refining and processing industry because it has good shape selective catalysis performance and very high cracking reaction activity.Along with day by day exhausting and the requirement of the aspect such as environmental protection of petroleum resources; particularly crude oil becomes heavy growth trend (high boiling component of＞500 ℃ increases) and market increasingly to the wilderness demand of light-end products; more and more pay attention to the deep processing to heavy oil and residual oil in PETROLEUM PROCESSING industry; the part refinery begins to mix refining decompression residuum, even directly take reduced crude as cracked stock.Traditional micro porous molecular sieve catalysis material is because its duct is less, larger raw molecule is demonstrated obvious restriction diffusion, cause the apparent reaction activity decreased, limit to a great extent macromolecular catalytic reaction, therefore be not suitable for being applied to the catalytic cracking reaction of the heavy ends such as heavy oil and residual oil.
For the heavy oil that improves catalytic cracking selective, the large molecule of heavy oil fraction is transformed, also will reduce simultaneously the further conversion of intermediate oil and naphtha, this just needs to use the aperture larger, reactant molecule is not had diffusion restriction, and have the material of higher cracking activity.And traditional micro porous molecular sieve only is beneficial to micromolecular cracking, and therefore mesoporous the and research and development macropore catalysis material more and more are subject to people's attention.
The appearance of mesopore molecular sieve is in 1992, at first succeeds in developing (BeckJ S, Vartuli J Z by U.S. Mobil company, Roth W J et al., J.Am.Chem.Comm.Soc., 1992,114,10834-10843), called after M41S series mesopore molecular sieve, comprise MCM-41 (MobilCorporation Material-41) and MCM-48 etc., the aperture of molecular sieve can reach 1.6～10nm, and is evenly adjustable, and pore-size distribution is concentrated, specific area and pore volume are large, high adsorption capacity; But because the hole wall structure of this molecular sieve analog is undefined structure, thus hydrothermal stability poor and acid a little less than, can't satisfy the operating condition of catalytic cracking, commercial Application is very restricted.
For solving the poor problem of mesopore molecular sieve hydrothermal stability, part Study work concentrates on and improves the molecular sieve pore wall thickness, as adopts neutral template can obtain the thicker molecular sieve of hole wall, but acid weak shortcoming still exists.A kind of novel mesopore molecular sieve is disclosed in CN 1349929A, introduce the primary and secondary construction unit of zeolite in the molecular sieve hole wall, make its basic structure with traditional zeolite molecular sieve, this mesopore molecular sieve has the hydrothermal stability of highly acid and superelevation.But the deficiency of this molecular sieve is need to use expensive template, and only there is the 2.7nm left and right in the aperture, still has larger space steric effect for large molecule cracking reaction, and under the high-temperature water heat condition, structure is easily subsided, and cracking activity is relatively poor.
In the catalytic cracking field, silica-alumina material due to its have stronger acid centre and well cracking performance used widely.The proposition of mesoporous concept, again for the preparation of new catalyst provide may, present result of study focuses mostly on and is using expensive organic formwork agent and organosilicon source, and majority will pass through high temperature hydro-thermal last handling process.Disclose a kind of monodisperse mesoporous aluminium silicon composite material in US5051385, added alkali after first acid inorganic aluminate and Ludox being mixed, obtained the aluminium content of silica-alumina material at 5～40 heavy %, the aperture is between 20～50nm, and specific area reaches 50～100m
2/ g.In US4708945, disclosed method is load silicon oxide particle or hydrated silica on the porous boehmite, again with the gained compound in hydrothermal treatment consists more than 600 ℃, make silica supportedly at the lip-deep catalyst of class boehmite, the surface area of this material is 100～200m
2/ g, average pore size 7～7.5nm.Disclose serial sour Cracking catalyst in US4440872, the carrier of some of them catalyst is by at γ-Al
2O
3Then upper dipping silane make after 500 ℃ of roastings or steam treatment.US2394796 discloses dipping silicon tetrachloride or silicon tetraethyl on the porous hydrated alumina, then obtains aluminium silicon composite material through hydrolysis.Adopting inorganic aluminate and waterglass in CN 1353008 is raw material, forms stable silicon-aluminum sol clearly through processes such as precipitation, dispergation, obtains white gels by drying, and roasting obtained Si-Al catalysis material after 1～20 hour under 350 ℃～650 ℃ conditions.US6858555 discloses a kind of catalyst for cracking heavy oil that contains mixed-metal oxides such as sieve and silica-sesquioxide, and wherein sieve and silica-sesquioxide is undefined structure.
Disclose a kind of mesoporous silica-alumina materials in CN1565733A, this silica-alumina material has the boehmite crystal phase structure, and pore-size distribution is concentrated, and specific area is 200～400m approximately
2/ g, pore volume 0.5～2.0ml/g, average pore size is between 8～20nm, and the most probable aperture is 5～15nm.The preparation of this mesoporous silica-alumina materials need not used organic formwork agent, and synthetic cost is low, and the silica-alumina material that obtains has high cracking activity and hydrothermal stability, shows good large molecule cracking performance in catalytic cracking reaction.
In the preparation technology of existing catalytic cracking catalyst, the colloid solid content of catalyst often is controlled at 25～28% left and right, and high solids content generally can reach 33～35% left and right, is difficult to further improve the colloid solid content under existing process conditions again.
Summary of the invention
The catalytic cracking catalyst that the purpose of this invention is to provide a kind of high solids content, low cost, high heavy oil conversion performance.
Cracking catalyst provided by the invention mainly is comprised of cracking activity constituent element, clay, binding agent and a kind of mesoporous silica-alumina materials.Specifically, mainly by the cracking activity constituent element of 5～70 heavy %, the mesoporous silica-alumina materials of the binding agent of the clay of 5～80 heavy %, 5～30 heavy % and 3～40 heavy % forms Cracking catalyst provided by the invention.
The content of said cracking activity constituent element in catalyst is 5～70 heavy %, and preferred 15～60 heavy % comprise Y zeolite, can also contain MFI structure Si-Al molecular sieve and/or beta zeolite etc.
Said Y zeolite is selected from one or more the mixture in HY, USY, REUSY, REY, REHY, REDASY, or the Y zeolite that obtains through various metal oxide treated.Content of rare earth in the said Y zeolite (REUSY, REY, REHY, REDASY) that contains rare earth is with RE
2O
3Count 0.5～20 heavy %.
Said MFI structure molecular screen can be selected from ZSM-5 zeolite or belong to the Si-Al molecular sieve of MFI structure with it together, 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 in CN1093101A).When containing MFI structure molecular screen and/or bet a zeolite in said cracking activity constituent element, having the Si-Al molecular sieve of MFI structure and the weight ratio of Y zeolite is 0.025～1, preferred 0.1～0.5; The weight ratio of beta zeolite and Y zeolite is 0.025～0.8.
Said clay is selected from the various clays that can be used as catalytic component, and as kaolin, imvite, bentonite etc., its content in catalyst is 5～80 heavy %, preferred 15～60 heavy %.
Said binding agent can be selected from one or both the mixture in Ludox and aluminium colloidal sol, preferred aluminium colloidal sol.The content of said binding agent in catalyst is with SiO
2And/or Al
2O
3Meter is 5～30 heavy %, preferred 8～25 heavy %.
Said mesoporous silica-alumina materials has the boehmite crystal phase structure, take the anhydrous chemical expression of oxide weight as (0-0.3) Na
2O (40-90) Al
2O
3(10-60) SiO
2, specific area is 200～400m
2/ g, pore volume is 0.5～2.0ml/g, preferred 1.0～2.0ml/g, and average pore size is 8～20nm, preferred 10～20nm, and the most probable aperture is 5～15nm, preferred 10～15nm, this mesoporous silica-alumina materials has detailed explanation in CN1565733A, this numerous stating no longer.The content of said mesoporous silica-alumina materials in catalyst is 3～40 heavy %, preferred 5～30 heavy %.
Catalyst provided by the invention is after Y zeolite or Y zeolite and MFI structure molecular screen and/or beta zeolite and clay, binding agent and mesoporous silica-alumina materials are mixed, to make through spraying, roasting, washing, drying.Control catalyst colloid solid content 30～50%, preferred 35～45% in catalyst preparation process.
Catalyst provided by the invention has following advantage:
At first, catalyst does not contain boehmite in forming, and in preparation process, the colloid solid content is high, effectively improves Catalyst Production efficient, has reduced production cost.
Secondly, production cost and the boehmite of said mesoporous silica-alumina materials are suitable, but the cracking activity of mesoporous silica-alumina materials is apparently higher than boehmite, compare with the conventional catalyst that uses boehmite, add the mesoporous silica-alumina materials of low amount can reach the cracking activity of the conventional catalyst that uses boehmite in Cracking catalyst provided by the invention, so further reduced again production cost.
The 3rd, the catalyst heavy oil conversion performance is strong.Can find out from the little anti-data of heavy oil, catalyst provided by the invention effectively improves the crude oil conversion capability simultaneously because can significantly reduce the heavy oil yield adding of mesoporous silica-alumina materials.
The specific embodiment
The following examples illustrate the present invention further, but content not thereby limiting the invention.
In each embodiment, the Na of mesoporous material used
2O, Al
2O
3, SiO
2Content and the content of rare earth in catalyst measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with x-ray fluorescence method.
The catalyst that is used for the heavy oil micro anti-evaluation needs in advance on the fixed bed aging equipment in 800 ℃, and under 100% steam, burin-in process is 17 hours.
The little anti-appreciation condition of heavy oil is: oil ratio 2.94, and catalyst inventory 5g, 500 ℃ of reaction temperatures, 600 ℃ of regeneration temperatures, feedstock oil is vacuum gas oil (VGO).
Embodiment 1
The preparation of catalyst CAT-1: with kaolin slurry (content is 40 heavy %, and China Kaolin Co., Ltd produces), aluminium colloidal sol (Al
2O
3The heavy % of content 21.5, the Shandong catalyst plant is produced), mesoporous silica-alumina materials SA-1, and REHY molecular sieve (RE
2O
312.3 heavy %, Na
2The heavy % of O 5.1, silica alumina ratio 4.7, the Shandong catalyst plant is produced) and a certain amount of deionized water mixing making beating, the colloid solid content is 35% left and right approximately, stirs 30 minutes, and then spray-drying is made microspherical catalyst.With this microspherical catalyst 500 ℃ of lower roastings 1 hour, then in 60 ℃ with (NH
4)
2SO
4Washing ((NH
4)
2SO
4: catalyst: H
2O=0.5: 1: 10) to Na
2The heavy % in O＜0.25 uses a large amount of deionized water drip washing at last, in 110 ℃ of oven dry, obtains catalyst CAT-1 after filtering.
Wherein mesoporous silica-alumina materials adopts the mesoporous silica-alumina materials SA-1 of embodiment 1 in CN1565733A, and the chemical composition of SA-1 is 0.12Na
2O73.7 Al
2O
326.2 SiO
2, its specific area is 362m
2/ g, pore volume are 1.19ml/g, and average pore size is 12.8nm, and the most probable aperture is 10nm.
Catalyst CAT-1 consists of: REHY molecular sieve 35.0%, kaolin 52.0%, aluminium colloidal sol 8.0%, mesoporous silica-alumina materials SA-1 5.0%.
The heavy oil evaluation result sees Table 1.
Embodiment 2～5
Embodiment 2～5th, illustrate with the impact of the different component in mesoporous silica-alumina materials replacement catalyst on the catalyst cracking performance.
The detailed process of spray catalyst is with embodiment 1, but the mixture that replaces respectively one or both or three in active component molecular sieve, kaolin and binding agent in preparation process with mesoporous silica-alumina materials, and regulate catalyst colloid solid content between 35～45%, make catalyst CAT-2～CAT-5.
Catalyst CAT-2 consists of: REHY molecular sieve 35.0%, kaolin 40.0%, aluminium colloidal sol 10.0%, mesoporous silica-alumina materials SA-1 15.0%.
Catalyst CAT-3 consists of: REHY molecular sieve 35.0%, kaolin 26.0%, aluminium colloidal sol 14.0%, mesoporous silica-alumina materials SA-1 25.0%.
Catalyst CAT-4 consists of: REHY molecular sieve 30.0%, kaolin 52.0%, aluminium colloidal sol 8.0%, mesoporous silica-alumina materials SA-1 10.0%.
Catalyst CAT-5 consists of: REHY molecular sieve 30.0%, kaolin 38.0%, aluminium colloidal sol 12.0%, mesoporous silica-alumina materials SA-1 20.0%.
The heavy oil evaluation result sees Table 1.
Comparative Examples 1
The preparation of comparative catalyst DB-1: with boehmite (the heavy % of solid content 65.8, Shandong Aluminum Plant produces) add in quantitative deionized water, after stirring, adding concentration is that 36% hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) carries out acidification, and sour aluminum ratio is controlled at 0.15～0.2, this moment, slurry pH value was about 1.0～1.2, stir after 40 minutes, be warming up to 65 ℃ of static acidifyings 1 hour, this moment, slurry pH value was about 3.0.After stopped heating, then add respectively kaolin slurry (content is 40 heavy %, and China Kaolin Co., Ltd produces) and aluminium colloidal sol (Al
2O
3The heavy % of content 21.5, the Shandong catalyst plant is produced), stir after 20 minutes, then add the REHY molecular sieve in mixed serum, continue to stir 20 minutes, then spray-drying is made microspherical catalyst.With this microspherical catalyst 500 ℃ of lower roastings 1 hour, then in 60 ℃ with (NH
4)
2SO
4Washing ((NH
4)
2SO
4: catalyst: H
2O=0.5: 1: 10) to Na
2The heavy % in O＜0.25 uses a large amount of deionized water drip washing at last, in 110 ℃ of oven dry, obtains comparative catalyst DB-1 after filtering.
Comparative catalyst DB-1 consists of: REHY molecular sieve 35.0%, kaolin 40.0%, aluminium colloidal sol 10.0%, boehmite 15.0%.
The heavy oil evaluation result sees Table 1.
Comparative Examples 2
The preparation process of comparative catalyst DB-2 is with Comparative Examples 1.
Comparative catalyst DB-2 consists of: REHY molecular sieve 35.0%, kaolin 26.0%, aluminium colloidal sol 14.0%, boehmite 25.0%.
The heavy oil evaluation result sees Table 1.
Table 1
| Catalyst | CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | DB-1 | DB-2 |
| Material balance, m% | |||||||
| Dry gas | 1.74 | 2.01 | 2.15 | 1.90 | 2.08 | 1.81 | 1.89 |
| Liquefied gas | 9.19 | 10.97 | 13.33 | 10.52 | 11.86 | 9.74 | 10.92 |
| Gasoline | 44.66 | 48.91 | 52.71 | 47.01 | 50.79 | 45.50 | 47.78 |
| Diesel oil | 22.27 | 21.68 | 20.34 | 22.04 | 21.09 | 22.13 | 21.95 |
| Heavy oil | 17.49 | 11.65 | 6.31 | 13.83 | 9.17 | 16.12 | 12.23 |
| Coke | 4.66 | 4.78 | 5.16 | 4.70 | 5.01 | 4.70 | 5.23 |
| Conversion ratio/m% | 60.24 | 66.67 | 73.35 | 64.13 | 69.74 | 61.75 | 65.82 |
| Yield of light oil/m% | 66.93 | 70.59 | 73.05 | 69.05 | 71.88 | 67.63 | 69.73 |
| Light receipts+liquefied gas/m% | 76.12 | 81.56 | 86.38 | 79.57 | 83.74 | 77.37 | 80.65 |
Can be found out by the heavy oil evaluation result, after adding mesoporous silica-alumina materials in catalyst, the conversion capability of catalyst significantly improves, and the heavy oil yield obviously reduces.The cracking activity that contains the catalyst CAT-1 of 5% mesoporous silica-alumina materials just can reach the cracking activity of the comparative catalyst DB-1 that contains 15% boehmite substantially; And the cracking activity that contains the catalyst CAT-2 of 15% mesoporous silica-alumina materials has surpassed the cracking activity of the comparative catalyst DB-2 that contains 25% boehmite, and heavy oil conversion performance also significantly improves.
Embodiment 6～8
The preparation process of the catalyst in embodiment 6～8 is with embodiment 1, but in preparation process cracking activity constituent element molecular screening with Y zeolite, ZSM-5 molecular sieve (Na
2O 2.8%, silica alumina ratio 60, the Shandong catalyst plant is produced) and beta zeolite (silica alumina ratio 30, the production of Shandong catalyst plant) in one or both or three's mixture, and regulate catalyst colloid solid content between 35～45%, make catalyst CAT-6, CAT-7, CAT-8.
Catalyst CAT-6 consists of: REHY molecular sieve 32.0%, ZSM-5 molecular sieve 3.0%, kaolin 40.0%, aluminium colloidal sol 10.0%, mesoporous silica-alumina materials SA-1 15.0%.
Catalyst CAT-7 consists of: REY molecular sieve (RE
2O
314.0%, Na
2O 3.2%, and silica alumina ratio 5.4, the Chang Ling catalyst plant is produced) 30.0%, beta molecular sieve 5.0%, kaolin 33.0%, aluminium colloidal sol 12.0%, mesoporous silica-alumina materials SA-1 20.0%.
Catalyst CAT-8 consists of: REUSY molecular sieve (RE
2O
31.6%, Na
2O 1.2%, and silica alumina ratio 6.8, the Shandong catalyst plant is produced) 30.0%, ZSM-5 molecular sieve 3.0%, beta molecular sieve 2.0%, kaolin 40.0%, aluminium colloidal sol 10.0%, mesoporous silica-alumina materials SA-1 15.0%.
The heavy oil evaluation result sees Table 2.
Table 2
| Catalyst | CAT-6 | CAT-7 | CAT-8 |
| Material balance, m% | |||
| Dry gas | 1.97 | 2.02 | 1.84 |
| Liquefied gas | 11.96 | 12.57 | 12.01 |
| Gasoline | 48.65 | 50.38 | 47.62 |
| Diesel oil | 21.92 | 21.01 | 22.23 |
| Heavy oil | 11.98 | 8.95 | 11.85 |
| Coke | 4.52 | 5.07 | 4.45 |
| Conversion ratio/m% | 66.10 | 70.04 | 65.92 |
| Yield of light oil/m% | 70.57 | 71.39 | 69.85 |
| Light receipts+liquefied gas/m% | 82.53 | 83.96 | 81.86 |
Embodiment 9～10
Mesoporous silica-alumina materials adopts the mesoporous silica-alumina materials SA-2 of embodiment 2 in CN1565733A.The chemical composition of SA-2 is 0.09 Na
2O59.1 Al
2O
340.8 SiO
2, its specific area is 315m
2/ g, pore volume are 1.26ml/g, and average pore size is 14.5nm, and the most probable aperture is 12nm.
Preparation process is with embodiment 1, and adjusting catalyst colloid solid content obtains catalyst CAT-9～10 between 35～45%.
Catalyst CAT-9 consists of: REHY 35.0%, kaolin 47.0%, aluminium colloidal sol 8.0%, mesoporous silica-alumina materials SA-2 10.0%.
Catalyst CAT-10 consists of: REUSY 30.0%, kaolin 33.0%, aluminium colloidal sol 12.0%, mesoporous silica-alumina materials SA-2 25.0%.
The heavy oil evaluation result sees Table 3.
Table 3
| Catalyst | CAT-9 | CAT-10 |
| Material balance, m% | ||
| Dry gas | 1.89 | 2.10 |
| Liquefied gas | 11.01 | 12.87 |
| Gasoline | 47.58 | 51.44 |
| Diesel oil | 21.30 | 20.69 |
| Heavy oil | 13.50 | 7.86 |
| Coke | 4.72 | 5.04 |
| Conversion ratio/m% | 65.20 | 71.45 |
| Yield of light oil/m% | 68.88 | 72.13 |
| Light receipts+liquefied gas/m% | 79.89 | 85.00 |
Claims (8)
1. Cracking catalyst that contains mesoporous silica-alumina materials, it is characterized in that this catalyst is comprised of cracking activity constituent element, clay, binding agent and mesoporous silica-alumina materials, said mesoporous silica-alumina materials wherein, has the boehmite crystal phase structure, take the anhydrous chemical expression of oxide weight as (0-0.3) Na
2O (40-90) Al
2O
3(10-60) S i O
2, specific area is 200～400m
2/ g, pore volume is that 0.5～2.0ml/g, average pore size are that 8～20nm, most probable aperture is 5～15nm, said binding agent is selected from one or both the mixture in Ludox and aluminium colloidal sol, and this catalyst is controlled catalyst colloid solid content 30～50% in preparation process.
2. according to the Cracking catalyst of claim 1, it is characterized in that this catalyst by the cracking activity constituent element of 5～70 heavy %, the mesoporous silica-alumina materials of the binding agent of the clay of 5～80 heavy %, 5～30 heavy % and 3～40 heavy % forms, and said binding agent is with SiO
2And/or Al
2O
3Meter.
3. according to the Cracking catalyst of claim 1, wherein, the cracking activity constituent element is Y zeolite, is perhaps the mixture of Y zeolite and MFI structure Si-Al molecular sieve and/or beta zeolite.
4. according to the Cracking catalyst of claim 3, said Y zeolite is selected from one or more the mixture in HY, USY, REUSY, REY, REHY, REDASY, or the Y zeolite that obtains through various metal oxide treated.
5. according to the Cracking catalyst of claim 4, wherein, in said REUSY, REY, REHY, REDASY, content of rare earth is with RE
2O
3Count 0.5～20 heavy %.
6. according to the Cracking catalyst of claim 3, wherein, said MFI structure molecular screen is selected from ZSM-5 zeolite or belongs to the Si-Al molecular sieve of MFI structure with it together.
7. according to the Cracking catalyst of claim 6, said ZSM-5 zeolite is through rare earth modified or through rare earth and phosphorus modification.
8. according to the Cracking catalyst of claim 3, wherein, when containing MFI structure molecular screen and/or beta zeolite in said cracking activity constituent element, the Si-Al molecular sieve of MFI structure and the weight ratio of Y zeolite are that the weight ratio of 0.025～1, beta zeolite and Y zeolite is 0.025～0.8.
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