CN100510015C - Production of cracking catalyst for preventing from heavy metal pollution - Google Patents
Production of cracking catalyst for preventing from heavy metal pollution Download PDFInfo
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- CN100510015C CN100510015C CNB2005100681795A CN200510068179A CN100510015C CN 100510015 C CN100510015 C CN 100510015C CN B2005100681795 A CNB2005100681795 A CN B2005100681795A CN 200510068179 A CN200510068179 A CN 200510068179A CN 100510015 C CN100510015 C CN 100510015C
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Abstract
It is a preparation method of cracking catalyst which can resist heavy metal pollution. Making clay, de-ionized water and optional additive well blended to get clay slurry. Making molecular screen de-ionized water and optional additive well blended to get molecular screen slurry. Making agglomerant, de-ionized water, alkali soil metal compound, rare earth compound and optional inorganic acid well blended to get agglomerant slurry. Uniform mixing three kinds of slurry mentioned before, and then drying the mixture. This kind of cracking catalyst has good resistivity to nickel and vanadium, and even when there is a high level of nickel in the catalyst, the cracking catalyst can work well.
Description
Technical field
The invention belongs to a kind of preparation method of hydrocarbon cracking catalyzer.
Technical background
Because national conditions institutes extremely, most of oil refining enterprises of China are limited for the range of choice of stock oil, as the former wet goods that oil fields such as grand celebration, triumph, the Liaohe River produce, have all suffered from the stock oil of high nickel content at present, wherein the nickel content in some crude oil has reached 15, more than the 000ppm.Can be deposited on the catalyst surface and mix metal pollutants such as Ni-V-Fe contained in the slag crude oil, copper, cause the poisoning of catalyst inactivation, thereby make the selectivity variation, yield of light oil descends, and hydrogen and coke yield rise.
Because the hydrofining of refinery is limited in one's ability, can not satisfy the demand of actual production far away, thereby cause the above-mentioned heavy metal content in the charging of catalytic cracking (FCC) device very high, require catalytic cracking catalyst to have very strong preventing from heavy metal pollution ability.
For prior art, the relevant report that addresses this problem occurs now and then, and summary is got up, and the method that reduces metallic pollutions such as nickel, vanadium on the catalyzer roughly has following three kinds:
One, the FCC metal passivator that adds liquid.As CN1068588 a kind of metal passivator of the FCC of being used for catalyzer is disclosed, the mixing solutions of the good fluidity of being made up of carboxylic compound (I), reaction medium (II) and solubilizing agent (III) three parts of antimony and/or bismuth; CN1294173 also is a kind of water-soluble metal passivator, is main ingredient with antimony, aluminium and Rare Earth Lanthanum (or cerium), can reduce the poisoning of catalyst inactivation significantly, improves gasoline and light oil yield, obviously reduces hydrogen yield and hydrogen/methane; JP01284580 discloses a kind of solution made from the salt of antimony, add this solution after, can reduce the generation of hydrogen, coke.Though effect is good, but contain in these liquid, be unfavorable for applying the disadvantageous component of environment.
Two, in catalyzer, add the solid nickel of solid, vanadium component.Some technology is to add the lanthanon of a kind of free or chemical combination form in raw material at least, or has added lanthanon or compound in the catalyst preparation process, as CN85106050A, and US4921824, EP347248, JP07126661; Some is to add element or compounds such as bismuth, antimony, tin, phosphorus in catalyst preparation process, as CN88102585, and EP303372, US4585545, EP141988, US4504381; Also some technology is element or the compound that has added alkaline-earth metal, copper, zinc, cadmium, tungsten, as EP461851, US4944865, US4944864, US4824815, EP303372, JP61235491, US4504381, US4290919, improve the heavy oil cracking performance of catalyzer, reduced the generation trend of hydrogen, coke simultaneously.But the heavy metal content in its raw material is less than 10, and the 000ppm nickel equivalent can't satisfy demand now.
Three, also has a kind of blunt nickel mode, as US4522704, US4504379 is disclosed to be between the reactor of catalytic cracking unit and revivifier special passive area to be set, to reduce the influence of pollution metal to catalyzer, because it is bigger that the equipment of being done is changed, need a large amount of investments, so so far, do not see that domestic device has relevant application report.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cracking catalyst of preventing from heavy metal pollution.
Preparation of catalysts method provided by the invention comprises:
(1), the preparation of clay slurry
Clay, deionized water and optional additive are mixed, make clay slurry, the add-on of additive is counted the heavy % of 0-3.0 with the butt weight of catalyzer;
(2), the preparation of molecular sieve pulp
Molecular sieve, deionized water and optional additive are mixed, make molecular sieve pulp, the add-on of additive is counted the heavy % of 0-1.0 with the butt weight of catalyzer;
(3), the preparation of binding agent slurries
Binding agent, deionized water, alkaline earth metal compound and rare earth compound are mixed, make the binding agent slurries, alkaline earth metal compound and rare earth compound all account for the heavy % of 0.05-5 of catalyzer butt weight in its oxide compound;
(4), the mixing of slurries
Above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed after drying.
Cracking catalyst by method preparation of the present invention has good anti-nickel, pollution of vanadium ability, when nickel content is higher on the catalyzer, still can keep high transformation efficiency and yield of light oil.
Embodiment
Preparation of catalysts method provided by the invention comprises:
(1), the preparation of clay slurry
Clay, deionized water and optional additive are mixed, make clay slurry, the add-on of additive is counted the heavy % of 0-3.0 with the butt weight of catalyzer;
(2), the preparation of molecular sieve pulp
Molecular sieve, deionized water and optional additive are mixed, make molecular sieve pulp, the add-on of additive is counted the heavy % of 0-1.0 with the butt weight of catalyzer;
(3), the preparation of binding agent slurries
Binding agent, deionized water, alkaline earth metal compound and rare earth compound are mixed, make the binding agent slurries, alkaline earth metal compound and rare earth compound all account for the heavy % of 0.05-5 of catalyzer butt weight in its oxide compound;
(4), the mixing of slurries
Above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed after drying.
The preparation of clay slurry, molecular sieve pulp and binding agent slurries does not have strict precedence, can prepare simultaneously, can be by the preparation of different order yet.
Cracking catalyst by method preparation of the present invention comprises the heavy % clay of 20-70, the heavy % molecular sieve of 15-50, the heavy % binding agent of 7-45, heavy % alkaline earth metal oxide of 0.05-5.0 and the heavy % rare-earth oxide of 0.05-5.0,0-4.0 heavy % additive is all in catalyzer butt weight.
Described clay is selected from one or more the mixture in kaolin, halloysite, polynite, diatomite, wilkinite, the sepiolite, preferred kaolin.
One or more the mixture of described molecular screening in faujusite, zeolite, mordenite, β zeolite with MFI structure.
Described faujusite is selected from y-type zeolite or/and X type zeolite, and wherein y-type zeolite is selected from one or more the mixture in phosphorated y-type zeolite, REY type zeolite, phosphorated REY type zeolite, HY type zeolite, phosphorated HY type zeolite, REHY type zeolite, phosphorated REHY type zeolite, USY type zeolite, phosphorated USY type zeolite, REUSY type zeolite, the phosphorated REUSY type zeolite; The zeolite of the described MFI of having structure is selected from ZSM-5, and is phosphorous or/and the mixture of one or more in the zeolite with MFI structure of rare earth.
In described clay slurry and/or molecular sieve pulp preparation process, add additive, this additive is selected from one or more the mixture in the multipolymer of homopolymer, band carboxyl chain link of soluble silicate, condensed phosphate, phosphonate, aminopolycanboxylic acid's salt, band carboxyl chain link, the mixture of one or more among optimization polypropylene acid sodium, ammonium polyacrylate, sodium-metaphosphate, trisodium phosphate or the water glass.
Described " optional additive " is meant that at least a slurry preparation process will add above-mentioned additive in described clay slurry, molecular sieve pulp.
Described binding agent is selected from a kind of or wherein several mixture in the silica-alumina gel of silicon-aluminum sol, silica-alumina gel, modification of aluminium colloidal sol, silicon sol, pseudo-boehmite, silicon-aluminum sol, modification, a kind of or wherein several mixture in preferred aluminium colloidal sol, silicon sol, the pseudo-boehmite, the mixture of preferred aluminium colloidal sol and pseudo-boehmite.
When binding agent contains pseudo-boehmite, must add mineral acid and carry out acidifying, described mineral acid is hydrochloric acid, nitric acid or phosphoric acid, preferred hydrochloric acid.
In described binding agent slurry preparation process, add alkaline earth metal compound, described alkaline earth metal compound is water miscible alkaline earth salt, is selected from one or more the solution of mixture in magnesium chloride, calcium chloride, bariumchloride, magnesium nitrate, nitrocalcite, the magnesium nitrate.
The solution that also adds rare earth compound in described binding agent slurry preparation process, described rare earth compound are that rare earth chloride is or/and rare earth nitrate, preferably rare earth chloride.
Preparation method provided by the invention has following characteristics:
1, the cracking catalyst of this method preparation has good anti-nickel, pollution of vanadium ability, when nickel content is higher on the catalyzer, still can keep high transformation efficiency and yield of light oil.Under the condition of high temperature and water vapor existence, alkaline-earth metal that adds in the binding agent slurries and thulium have played the effect that activates aluminum oxide, can form the solid metal salts with nickel, vanadium etc., and be fixed, to reduce its destruction.
2, behind the adding additive, improved the solid content of clay slurry and molecular sieve pulp respectively, according to catalyst formulation clay, molecular sieve and three strands of slurries of binding agent are mixed forming catalyst slurry again, this one-tenth glue mode makes Preparation of catalysts become more flexible, and is quick and easy to control.
3, the catalyzer of this method preparation has bigger pore volume, this means the green coke trend that can reduce crackate, improves product and distributes.
The following examples will the present invention will be further described, but therefore do not limit the present invention.
Among the embodiment, nickel in the catalyst sample, vanadium, calcium, magnesium, barium and content of rare earth are measured with fluorometry, phosphorus content is measured with chemical colorimetry, the pore volume employing " the petrochemical complex analytical procedure (the RIPP test method " (Yang Cuiding, Gu Kanying compile, 1990, Science Press) method of the RIPP28-90 in is measured.
The method of catalyzer nickel contamination is in the laboratory: by the ratio of prescription requirements with the kerosin impregnated catalyst of nickel naphthenate, 110 ℃ of dryings 4 hours down, 550 ℃ of following roastings 5 hours, to remove the whole organism on the catalyzer.
The method of catalyzer pollution of vanadium is in the laboratory: by the ratio of prescription requirements with the kerosin impregnated catalyst of naphthenic acid vanadium, 110 ℃ of dryings 4 hours down, 550 ℃ of following roastings 5 hours, to remove the whole organism on the catalyzer.
The catalyzer that is used for the little anti-and fixed fluidized bed evaluation of light oil is in advance through aging 4 hours, 8 hours or 17 hours of 800 ℃, 100% water vapour.
The little anti-appreciation condition of light oil is: it is the particle of 420-841 micron that catalyst breakage is become particle diameter, and loading amount is 5 grams, and reaction raw materials is that boiling range is 235-337 ℃ a straight distillation light diesel oil, 460 ℃ of temperature of reaction, and weight space velocity is 16 hours
-1, agent-oil ratio 3.2.
Be lower than gasoline yield+gas yield+coke yield of 204 ℃ in light oil microactivity MA=(being lower than gasoline output+gas yield+coke output of 204 ℃ in the product)/charging total amount * 100%=product.
Fixed fluidized bed appreciation condition is: the catalyzer loading amount is 90 grams, and reaction raw materials is a 80%VGO+20% vacuum residuum, 500 ℃ of temperature of reaction, and weight space velocity is 30 hours
-1, agent-oil ratio 3-6.
Embodiment 1
1.4 kilograms of kaolin (dry basis, China Kaolin Co., Ltd produces) are added 20 gram sodium polyacrylates, and (chemical experimental factory, Heze, Shandong produces, molecular weight 4,000-10,000) in the solution made from 1.0 kilograms of deionized waters, stirred the formation kaolin slurry 1.5 hours.
Get 1.0 kilograms of pseudo-boehmites (in aluminum oxide, Shandong Aluminum Plant produce), 0.4 kilogram of aluminium colloidal sol (in aluminum oxide, the Shandong catalyst plant is produced) after mixing with 4.0 kilograms of deionized waters, adds 91 milliliters of re chlorides and (makes RE by oneself
2O
3Concentration is 219 grams per liters, and the solid rare earth chloride is produced by Inner Mongol Baotou rare earth factory, RE
2O
3Content 46 heavy %, RE
2O
3Consist of La
2O
353.2 heavy %, CeO
213.0 heavy %, Pr
6O
1113.0 heavy %, Nd
2O
320.8 heavy %, down together) and 771 gram MgCl
26H
2In the aqueous solution of O (chemical pure, Beijing chemical reagents corporation product), the hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) that adds 200 milliliter of 36 heavy % again mixes to stir promptly finished acidization in 1.5 hours, and needn't heat up wears out can obtain the binding agent slurries.
Get 1.0 kilograms of REY molecular sieve (RE
2O
3Content 18.5 heavy %, Na
2O content is 1.6 heavy %, silica alumina ratio 5.4, the Shandong catalyst plant is produced) mix with 1.5 kilograms of deionized waters that add 15 gram Sodium hexametaphosphate 99s (chemical pure, Beijing chemical reagents corporation produces), obtain molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyst A 1 that promptly obtains by the present invention's preparation.Consisting of of catalyst A 1: kaolin 34.8 heavy %, pseudo-boehmite 25.0 heavy %, aluminium colloidal sol 10.0 heavy %, REY molecular sieve 25.0 heavy %, the heavy % of MgO3.8, RE
2O
30.5 heavy %, additive 0.9 heavy %.The character of catalyst A 1 is listed in the table 1.
Comparative Examples 1
This Comparative Examples is to prepare catalyzer by embodiment 1 described method, but does not add MgCl in the binding agent
26H
2O.
1.6 kilograms of kaolin are added in the solution that 12 gram sodium polyacrylates and 1.0 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.0 kilograms of pseudo-boehmites, 0.4 kilogram of aluminium colloidal sol after mixing with 3.8 kilograms of deionized waters, adds 91 milliliters of re chlorides, and the mixed in hydrochloric acid that adds 200 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours, obtained the binding agent slurries.
Get 1.0 kilograms of REY molecular sieves and mix, obtain molecular sieve pulp with 1.5 kilograms of deionized waters that add 15 gram Sodium hexametaphosphate 99s.
Above-mentioned three strands of slurries are mixed the spray-dried comparative catalyst A2 that promptly obtains.Comparative catalyst A2 consists of: kaolin 38.8 heavy %, pseudo-boehmite 25.0 heavy %, aluminium colloidal sol 10.0 heavy %, REY molecular sieve 25.0 heavy %, RE
2O
30.5 heavy %, additive 0.7 heavy %.The character of comparative catalyst A2 is listed in the table 1.
Comparative Examples 2
This Comparative Examples is to prepare catalyzer by embodiment 1 described method, but does not add the chlorination rare earth in the binding agent.
1.4 kilograms of kaolin are added in the solution that 12 gram sodium polyacrylates and 1.0 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.0 kilograms of pseudo-boehmites, 0.4 kilogram of aluminium colloidal sol after mixing with 4.0 kilograms of deionized waters, adds 771 gram MgCl
26H
2In the solution that O and 1.0 kg water generate, the mixed in hydrochloric acid that adds 200 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours, and needn't heat up wears out can obtain the binding agent slurries.
Get 1.0 kilograms of REY molecular sieves and mix, obtain molecular sieve pulp with 1.5 kilograms of deionized waters that add 15 gram Sodium hexametaphosphate 99s.
Above-mentioned three strands of slurries are mixed the spray-dried comparative catalyst A3 that promptly obtains.Comparative catalyst A3 consists of: kaolin 35.5 heavy %, pseudo-boehmite 25.0 heavy %, aluminium colloidal sol 10.0 heavy %, REY molecular sieve 25.0 heavy %, MgO 3.8 heavy %, additive 0.7 heavy %.The character of comparative catalyst A3 is listed in the table 1.
Comparative Examples 3
The explanation of this Comparative Examples does not add the preparation method of the conventional catalyst of additive.
1.6 kilograms of kaolin are added in 7.0 kilograms of deionized waters, stirred 1.5 hours, add 1.0 kilograms of pseudo-boehmites again, pull an oar after 0.5 hour, the hcl acidifying that adds 260 milliliter of 36 heavy % is warming up to 60～70 ℃ and wore out 1 hour after 20 minutes, add aluminium colloidal sol then and mix stirring 15 minutes for 0.4 kilogram, add the molecular sieve pulp of 1.0 kilograms of REY at last, the spray-dried comparative catalyst A4 that promptly obtains.
Comparative catalyst A4 consists of: kaolin 40.0 heavy %, pseudo-boehmite 25.0 heavy %, aluminium colloidal sol 10.0 heavy %, REY molecular sieve 25.0 heavy %.
The catalyst sample of above-mentioned preparation is carried out nickel, pollution of vanadium: in proportion with the kerosin impregnated catalyst of nickel naphthenate, naphthenic acid vanadium, 110 ℃ dry 4 hours down, 550 ℃ of roastings 5 hours.The related properties of comparative catalyst A4 are listed in the table 1.
Table 1
Annotate: liquid receipts=liquefied gas+gasoline+diesel oil,
*It is the light oil microactivity after polluting
Embodiment 2
1.3 kilograms of kaolin are added in the solution that 20 gram trisodium phosphates (chemical pure, Beijing chemical reagents corporation produces) and 1.5 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.2 kilograms of pseudo-boehmites, 0.2 kilogram of aluminium colloidal sol after mixing with 3.0 kilograms of deionized waters, adds 18 milliliters of re chlorides and 147 gram CaCl
22H
2In the aqueous solution of O (chemical pure, Beijing chemical reagents corporation produces), the mixed in hydrochloric acid that adds 140 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 1.2 kilograms of DASY
2.0Molecular sieve (a kind of REUSY zeolite, RE
2O
3Content 1.5 heavy %, Na
2O content is 1.2 heavy %, silica alumina ratio 6.8, the Shandong catalyst plant is produced, down together) mix with 1.5 kilograms of deionized waters that add 15 gram sodium polyacrylates, obtain molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyst B 1 that promptly obtains by the present invention's preparation.Consisting of of catalyst B 1: kaolin 33.7 heavy %, pseudo-boehmite 28.9 heavy %, aluminium colloidal sol 5.0 heavy %, DASY
20Molecular sieve 30.0 heavy %, the heavy % of CaO1.4, RE
2O
30.1 heavy %, additive 0.9 heavy %.The character of catalyst B 1 is listed in the table 2.
Comparative Examples 4
This Comparative Examples is according to disclosed preparation method among the CN1067670A embodiment 5, comparative catalyst's composition of preparation.
With 18 milliliters of re chlorides and 147 gram CaCl
22H
2O solution mixes, and adds 0.8 kilogram of γ-Al
2O
3(being made in 2 hours through 550 ℃ of roastings by pseudo-boehmite) stirs, 110 ℃ of dryings 4 hours, 600 ℃ of roastings 1 hour, vanadium fixing agent.
1.4 kilograms of kaolin are added in 5.0 kilograms of deionized waters, stirred 1.5 hours, add 0.4 kilogram of pseudo-boehmite again, pull an oar after 0.5 hour, the hcl acidifying that adds 120 milliliter of 36 heavy % is warming up to 60～70 ℃ and wore out 1 hour after 20 minutes, add aluminium colloidal sol then and mix stirring 15 minutes for 0.2 kilogram, add 1.2 kilograms of DASY at last
2.0Molecular sieve pulp, the spray-dried Primary Catalysts that obtains mixes with above-mentioned vanadium fixing agent again, promptly gets comparative catalyst B2.
Comparative catalyst B2 consists of: kaolin 35.0 heavy %, pseudo-boehmite 10.0 heavy %, aluminium colloidal sol 5.0 heavy %, DASY
2.0Molecular sieve 30.0 heavy %, vanadium fixing agent is formed γ-Al
2O
318.9 heavy %, the heavy % of Ca1.0, the heavy % of RE0.1.
The catalyst sample of above-mentioned preparation is carried out nickel, pollution of vanadium: in proportion with the kerosin impregnated catalyst of nickel naphthenate, naphthenic acid vanadium, 110 ℃ dry 4 hours down, 550 ℃ of roastings 5 hours.The character of comparative catalyst B2 is listed in the table 2.
Table 2
Embodiment 3
0.6 kilogram of kaolin is added in the solution that 150 gram water glass (produce in Red Star chemical plant, Beijing, modulus is 3.0) and 0.4 kilogram of deionized water make, stirred the formation kaolin slurry 1.5 hours.
Get 1.5 kilograms of pseudo-boehmites, 1.2 kilograms of aluminium colloidal sols after mixing with 4.0 kilograms of deionized waters, add 795 milliliters of re chlorides and 173 gram CaCl
22H
2In the aqueous solution of O, the mixed in hydrochloric acid that adds 200 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 1.9 kilograms of REHY molecular sieve (RE
2O
3Content is 8.4 heavy %, Na
2O content is 3.7 heavy %, silica alumina ratio 5.6, the Chang Ling catalyst plant is produced), 0.1 kilogram of ZRP-5 molecular sieve (a kind of zeolite, Na with MFI structure
2O content 0.1 heavy %, silica alumina ratio 50, the Shandong catalyst plant is produced, down together), 0.3 kilogram of beta-molecular sieve (silica alumina ratio 25, the Chang Ling catalyst plant is produced), (the Shandong catalyst plant is produced, molecular weight 4,000-20 with adding 40 gram ammonium polyacrylates, 000) 2.5 kilograms of deionized waters mix, and obtain molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyzer C1 that promptly obtains by the present invention's preparation.Catalyzer C1 consists of: kaolin 10.0 heavy %, pseudo-boehmite 24.4 heavy %, aluminium colloidal sol 19.8 heavy %, REHY molecular sieve 31.7 heavy %, ZRP-5 molecular sieve 2.0 heavy %, beta-molecular sieve 4.9 heavy %, the heavy % of CaO1.1, RE
2O
32.9 heavy %, additive 3.2 heavy %.The character of catalyzer C1 is listed in the table 3.
Comparative Examples 5
This Comparative Examples is according to disclosed preparation method among the CN1341697A embodiment 6, the comparative catalyst of preparation.
The solution of 8.7 gram Secondary ammonium phosphates is added in 2.0 kilograms of REHY molecular sieves, stir 5 hours mixings, 120 ℃ drying is after 1.5 hours down, and roasting is 3 hours in 575 ℃ of air.The phosphorous REHY molecular sieve that roasting is good, 0.1 kilogram of MFI structure molecular screen, 0.3 kilogram of beta-molecular sieve is made molecular sieve pulp with deionized water.
Take from 260 milliliters of system re chlorides, the ammoniacal liquor with 28% slowly adds and constantly stirs, and makes slurries pH value 9.1.
Get 0.6 kilogram of kaolin, add 4.0 kilograms of deionized water making beating, adding 1.6 kilograms of pseudo-boehmites then mixed after 2 hours, adding 919 gram HCl stirs, wore out 5 hours down at 70 ℃, add 1.1 kg aluminium colloidal sols again and mix after 1 hour, above-mentioned alkaline rare earth slurries adding is stirred, mix with molecular sieve pulp at last, promptly get comparative catalyst C2.Comparative catalyst C2 consists of: kaolin 10.0 heavy %, pseudo-boehmite 27.6 heavy %, aluminium colloidal sol 19.8 heavy %, REHY molecular sieve 31.7 heavy %, MFI type molecular sieve 2.0 heavy %, beta-molecular sieve 4.9 heavy %, P
2O
51.1 heavy %, RE
2O
32.9 heavy %.
The catalyst sample of above-mentioned preparation is carried out nickel, pollution of vanadium: in proportion with the kerosin impregnated catalyst of nickel naphthenate, naphthenic acid vanadium, 110 ℃ dry 4 hours down, 550 ℃ of roastings 5 hours.The character of comparative catalyst C2 is listed in the table 3.
Table 3
Embodiment 4
1.7 kilograms of kaolin are added in the solution that 30 gram Sodium hexametaphosphate 99s and 2.5 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.3 kilograms of pseudo-boehmites, 0.6 kilogram of aluminium colloidal sol after mixing with 4.0 kilograms of deionized waters, adds 932 milliliters of re chlorides and 96 gram BaCl
22H
2In the aqueous solution of O (chemical pure, Beijing chemical reagents corporation produces), the mixed in hydrochloric acid that adds 150 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 2.1 kilograms of DM-4 molecular sieves (a kind of USY type zeolite that contains rare earth, RE
2O
3Content is 3.4 heavy %, Na
2O content is 2.1 heavy %, silica alumina ratio 6.2, the Shandong catalyst plant is produced) mix with 2.8 kilograms of deionized waters that add 20 gram sodium polyacrylates, obtain molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyzer D that promptly obtains by the present invention's preparation.Catalyzer D consists of: kaolin 27.8 heavy %, pseudo-boehmite 22.0 heavy %, aluminium colloidal sol 10.0 heavy %, DM-4 molecular sieve 35.0 heavy %, the heavy % of BaO1.0, RE
2O
33.4 heavy %, additive 0.8 heavy %.The character of catalyzer D is listed in the table 4.
Embodiment 5
2.0 kilograms of kaolin are added in the solution that 35 gram Sodium hexametaphosphate 99s and 1.5 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.3 kilograms of pseudo-boehmites, 0.6 kilogram of aluminium colloidal sol after mixing with 4.0 kilograms of deionized waters, adds 1096 milliliters of re chlorides and 38 gram BaCl
22H
2In the aqueous solution of O, the mixed in hydrochloric acid that adds 150 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 1.8 kilograms of DASY
0.0Molecular sieve (a kind of USY zeolite, Na
2O content is 0.98 heavy %, silica alumina ratio 6.2, the Shandong catalyst plant is produced, down together) mix with 2.4 kilograms of deionized waters that add 20 gram sodium polyacrylates, obtain molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyzer E that promptly obtains by the present invention's preparation.Catalyzer E consists of: kaolin 32.7 heavy %, pseudo-boehmite 22.0 heavy %, aluminium colloidal sol 10.0 heavy %, DASY
0.0Molecular sieve 30.0 heavy %, the heavy % of BaO0.4, RE
2O
34.0 heavy %, additive 0.9 heavy %.The character of catalyzer E is listed in the table 4.
Embodiment 6
1.4 kilograms of kaolin are added in the solution that 30 gram trisodium phosphates and 1.5 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.2 kilograms of pseudo-boehmites, 0.9 kilogram of aluminium colloidal sol after mixing with 4.0 kilograms of deionized waters, adds 274 milliliters of re chlorides and 457 gram MgCl
26H
2In the aqueous solution of O, the mixed in hydrochloric acid that adds 150 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 0.6 kilogram of REHY molecular sieve, 1.7 kilograms of DASY
0.0Molecular sieve mixes with 4.0 kilograms of deionized waters that add 20 gram sodium polyacrylates, obtains molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyzer F that promptly obtains by the present invention's preparation.Catalyzer F consists of: kaolin 23.7 heavy %, pseudo-boehmite 20.0 heavy %, aluminium colloidal sol 15.0 heavy %, REHY molecular sieve 10.0 heavy %, DASY
0.0Molecular sieve 28.0 heavy %, MgO 1.5 heavy %, RE
2O
31.0 heavy %, additive 0.8 heavy %.The character of catalyzer F is listed in the table 4.
Embodiment 7
1.4 kilograms of kaolin are added in the solution that 30 gram trisodium phosphates and 1.5 kilograms of deionized waters make, stirred the formation kaolin slurry 1.5 hours.
Get 1.2 kilograms of pseudo-boehmites, 0.9 kilogram of aluminium colloidal sol after mixing with 4.0 kilograms of deionized waters, adds 274 milliliters of re chlorides and 762 gram MgCl
26H
2In the aqueous solution of O, the mixed in hydrochloric acid that adds 150 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 0.3 kilogram of REY molecular sieve, 2.0 kilograms of DASY
0.0Molecular sieve mixes with 4.5 kilograms of deionized waters that add 10 gram sodium polyacrylates, obtains molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyzer G that promptly obtains by the present invention's preparation.Catalyzer G consists of: kaolin 22.8 heavy %, pseudo-boehmite 20.0 heavy %, aluminium colloidal sol 15.0 heavy %, REY molecular sieve 5.0 heavy %, DASY
0.0Molecular sieve 33.0 heavy %, the heavy % of MgO2.5, RE
2O
31.0 heavy %, additive 0.7 heavy %.
The catalyst sample of above-mentioned preparation is carried out nickel, pollution of vanadium: with the kerosin impregnated catalyst of nickel naphthenate, naphthenic acid vanadium, drying was 4 hours under 110 ℃, 550 ℃ of following roastings 5 hours in proportion.The character of catalyzer G is listed in the table 4.
Table 4
Embodiment 8-11
1.4 kilograms of kaolin are added in the solution that 5 gram sodium polyacrylates, 15 gram trisodium phosphates and 0.8 kilogram of deionized water make, stirred the formation kaolin slurry 1.5 hours.
Get 1.2 kilograms of pseudo-boehmites, 0.7 kilogram of aluminium colloidal sol after mixing with 4.0 kilograms of deionized waters, adds 457 milliliters of re chlorides and 254 gram MgCl
26H
2In the aqueous solution of O, the mixed in hydrochloric acid that adds 200 milliliter of 36 heavy % again stirs promptly finished acidization in 1.5 hours.
Get 0.4 kilogram of beta-molecular sieve, 1.2 kilograms of DASY-1 (a kind of USY zeolite, Na
2O content is 4.0 heavy %, and silica alumina ratio 6.0, the Shandong catalyst plant is produced) molecular sieve mixes with 1.5 kilograms of deionized waters that add 15 gram sodium polyacrylates, obtains molecular sieve pulp.
Above-mentioned three strands of slurries are mixed the spray-dried catalyzer H that promptly obtains by the present invention's preparation.Catalyzer H consists of: kaolin 28.3 heavy %, pseudo-boehmite 23.0 heavy %, aluminium colloidal sol 13.0 heavy %, beta-molecular sieve 8.0 heavy %, DASY-1 molecular sieve 24.0 heavy %, the heavy % of MgO1.0, RE
2O
32.0 heavy %, additive 0.7 heavy %.
From the catalyst sample of above-mentioned preparation, take out three parts of H1, H2, H3, carry out nickel, the pollution of vanadium of different ratios respectively: with the kerosin impregnated catalyst of nickel naphthenate, naphthenic acid vanadium, drying is 4 hours under 110 ℃, 550 ℃ of roastings 5 hours, the character of four catalyzer H, H1, H2, H3 is listed in the table 5.
Table 5
| Catalyzer | H | H1 | H2 | H3 |
| Contamination level, ppm | ||||
| Ni | 0 | 3000 | 5000 | 6000 |
| V | 0 | 3000 | 1500 | 1000 |
| MA(800℃/4h) | 79 | 70 | 71 | 72 |
| Transformation efficiency, heavy % | 82.9 | 70.8 | 72.1 | 74.7 |
| Liquid is received, heavy % | 89.0 | 81.5 | 82.0 | 83.3 |
| Coke, heavy % | 7.6 | 7.8 | 8.5 | 8.7 |
| Hydrogen/methane | Do not detect | 1.0 | 1.4 | 1.5 |
Claims (10)
1, a kind of production of cracking catalyst of preventing from heavy metal pollution is characterized in that this method comprises:
(1), the preparation of clay slurry
Clay, deionized water and optional additive are mixed, make clay slurry, the add-on of additive is counted the heavy % of 0.4-3.0 with the butt weight of catalyzer, described clay is selected from one or more the mixture in kaolin, halloysite, polynite, diatomite, wilkinite, the sepiolite, and described additive is selected from one or more the mixture in the multipolymer of homopolymer, band carboxyl chain link of soluble silicate, condensed phosphate, phosphonate, aminopolycanboxylic acid's salt, band carboxyl chain link;
(2), the preparation of molecular sieve pulp
Molecular sieve, deionized water and optional additive are mixed, make molecular sieve pulp, the add-on of additive is counted the heavy % of 0.175-1.0 with the butt weight of catalyzer, one or more the mixture of described molecular screening in faujusite, the zeolite with MFI structure, mordenite, β zeolite, described additive are selected from one or more the mixture in the multipolymer of homopolymer, band carboxyl chain link of soluble silicate, condensed phosphate, phosphonate, aminopolycanboxylic acid's salt, band carboxyl chain link;
(3), the preparation of binding agent slurries
Binding agent, deionized water, alkaline earth metal compound and rare earth compound are mixed, make the binding agent slurries, alkaline earth metal compound and rare earth compound all account for the heavy % of 0.05-5 of catalyzer butt weight in its oxide compound, described alkaline earth metal compound is selected from one or more the mixture in magnesium chloride, calcium chloride, bariumchloride, magnesium nitrate, nitrocalcite, the magnesium nitrate, and described rare earth compound is that rare earth chloride is or/and rare earth nitrate;
(4), the mixing of slurries
Above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed after drying, three kinds of slurries blended ratios, the cracking catalyst that guarantees preparation comprises the heavy % clay of 20-70, the heavy % molecular sieve of 15-50, the heavy % binding agent of 7-45,0.05-5.0 the heavy % rare-earth oxide of heavy % alkaline earth metal oxide and 0.05-5.0, the heavy % additive of 0.575-4.0 is all in catalyzer butt weight.
2, method according to claim 1 is characterized in that described faujusite is selected from y-type zeolite or/and X type zeolite.
3, method according to claim 2 is characterized in that described y-type zeolite is selected from one or more the mixture in phosphorated y-type zeolite, REY type zeolite, HY type zeolite, REHY type zeolite, USY type zeolite, the REUSY type zeolite.
4, method according to claim 1 is characterized in that the zeolite of the described MFI of having structure is selected from ZSM-5, and is phosphorous or/and the mixture of one or more in the zeolite with MFI structure of rare earth.
5, method according to claim 1 is characterized in that described additive is selected from one or more the mixture among sodium polyacrylate, ammonium polyacrylate, sodium-metaphosphate, trisodium phosphate or the water glass.
6, method according to claim 1 is characterized in that described optional additive is meant that at least a slurry preparation process will add described additive in described clay slurry, molecular sieve pulp.
7, method according to claim 1 is characterized in that described binding agent is selected from one or more the mixture in aluminium colloidal sol, silicon sol, pseudo-boehmite, silicon-aluminum sol, the silica-alumina gel.
8, method according to claim 7 is characterized in that when binding agent contains pseudo-boehmite, must add mineral acid and carry out acidifying, and described mineral acid is hydrochloric acid or nitric acid.
9, method according to claim 3, it is characterized in that described REY type zeolite is a phosphorated REY type zeolite, described HY type zeolite is a phosphorated HY type zeolite, described REHY type zeolite is a phosphorated REHY type zeolite, described USY type zeolite is a phosphorated USY type zeolite, and described REUSY type zeolite is a phosphorated REUSY type zeolite.
10, method according to claim 7 is characterized in that described silicon-aluminum sol is the silicon-aluminum sol of modification, and described silica-alumina gel is the silica-alumina gel of modification.
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| CN101584991B (en) * | 2008-05-23 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof |
| CN103789013B (en) * | 2012-10-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
| CN104028298B (en) * | 2014-05-16 | 2016-08-17 | 茂名市茂群高岭土有限公司 | A kind of catalyst for heavy oil catalytic cracking using Maoming Kaolin to prepare |
| CN108404897B (en) * | 2017-02-10 | 2021-03-09 | 中国石油天然气股份有限公司 | Heavy oil hydrogenation catalyst carrier, preparation method thereof, catalyst using heavy oil hydrogenation catalyst carrier and preparation method of catalyst |
| CN108499600B (en) * | 2018-04-19 | 2021-03-30 | 润和催化剂股份有限公司 | Catalytic cracking catalyst for increasing diesel oil yield and preparation method thereof |
| CN115055203B (en) * | 2022-07-20 | 2024-10-18 | 成都蓉澄石化科技有限公司 | Heavy oil catalytic cracking catalyst |
| CN115555011A (en) * | 2022-08-24 | 2023-01-03 | 碳中能源科技(北京)有限公司 | Auxiliary agent for improving heavy metal pollution resistance of FCC (fluid catalytic cracking) catalyst |
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