CN100377784C - Metal modified SAPO-34 molecular screen and its uses - Google Patents

Metal modified SAPO-34 molecular screen and its uses Download PDF

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CN100377784C
CN100377784C CNB2004100802314A CN200410080231A CN100377784C CN 100377784 C CN100377784 C CN 100377784C CN B2004100802314 A CNB2004100802314 A CN B2004100802314A CN 200410080231 A CN200410080231 A CN 200410080231A CN 100377784 C CN100377784 C CN 100377784C
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molecular sieve
sapo
metal
transition metal
catalyst
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CN1754624A (en
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罗一斌
达志坚
欧阳颖
庄立
龙军
李黎生
王殿中
舒兴田
宗保宁
李明罡
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The present invention discloses a metal modified SAPO-34 molecular sieve. The present invention is characterized in that the chemistry expression of the molecular sieve without water is (0.1 to 15) M2O3. (0.9 to 72) Al2O3. (1 to 78) P2O5. (0.4 to 97) SiO2 according to the mass of oxide, wherein M is selected from one or two kinds of the transmission metal of Fe, Co and Ni. The molecular sieve is applied to the cracking process of petroleum hydrocarbon as an active component for catalysis; compared with the molecular sieve provided by the prior art, the present invention increases the yield and the selectivity of C2 to C4 olefins, and has higher yield of liquid gas.

Description

A kind of metal-modified SAPO-34 molecular sieve and application thereof
Technical field
The invention relates to a kind of molecular sieve and application thereof, the application of further saying so and under the cracking reaction condition, improving the product propylene content about a kind of metal-modified SAPO-34 molecular sieve and this molecular sieve thereof.
Technical background
The steam heat cracking of hydro carbons and catalytic cracking are the essential industry processes of producing propylene, and wherein the FCC apparatus propylene provides about 30% demand.Because output is huge, the very little improvement of operating efficiency will change into significant income.Catalyst plays an important role in conversion of olefines at the hydro carbons of high selectivity more.
The catalyst that contains mesopore zeolite can become naphtha pyrolysis little olefin hydrocarbon molecules such as ethene, propylene and butylene.As ZSM-5 zeolite:, in 758,403, disclosed the method for in catalytic cracking catalyst, adding the ZSM-5 molecular sieve and can improve the octane number of gasoline and increase C at USP3 with MFI structure 3-C 4The productive rate of alkene.USP4,922,051 have described the cracking of adopting the C2-C12 alkane that the composite catalyst that preferably includes 25%ZSM-5 carries out, and its conversion ratio contains at least 55% C2-4 and C6-C8 aromatic compounds greater than 90% in the product.The zeolite catalyst of this generic crystallized silicon aluminate has the patent of invention of a lot of this respects.
In addition, USP4,440,871 propose to come selectivity to produce light hydrocarbon and alkene with silicoaluminophosphate (SAPO) molecular sieve hydrocarbon cracking raw material.The SAPO molecular sieve has the AlO that is connected by oxygen atom 4, SiO 4And PO 4Tetrahedral network, intracrystalline duct, because of tetravalence Si replace that P (V) or Al (III) produce acid or replace Al (III) with metal M e (II) and produce acidity this molecular sieve is played an important role in separation and catalytic action.Propose among the CN1305445A under cracking condition hydro carbons contacted with SAPO, MeAPO (the metal isomorphous replaces the aluminium phosphorus molecular sieve of Al), MeASPO (the metal isomorphous replaces the sial phosphorus molecular sieve of Al) etc. and improve the optionally method that hydrocarbon raw material is cracked into propylene, propose especially SAPO-11 and SAPO-34 in the acquisition of hexene feed cracking process than the better propylene selectivity of ZSM-5.
But this area does not recognize that also the SAPO-34 molecular sieve that has only 3.8 * 3.8 dusts in the aperture is with the characteristic of metal-modified back at the hydrocarbon cracking conversion aspect.
Summary of the invention
One of purpose of the present invention provides a kind of metal-modified SAPO-34 molecular sieve, and two of purpose provides the application of this molecular sieve in cracking process.
Metal-modified SAPO-34 molecular sieve provided by the invention, its anhydrous chemical expression is counted (0.1～15) M with the quality of oxide xO y(0.9～72) Al 2O 3(1～78) P 2O 5(0.4～97) SiO 2, preferred (0.5～10) M xO y(5～50) Al 2O 3(10～70) P 2O 5(5～50) SiO 2, wherein, M is selected from one or both among transition metal Fe, Co and the Ni, preferred Fe, and x represents the atomicity of M, y represents to satisfy the required number of M oxidation state.
We know that the SAPO molecular sieve has PO 2 +, AlO 2 +And SiO 2The dimensional microporous crystal framework structure of tetrahedron element, chemical composition (anhydrous) is: mR:(Si xAl yP z) O 2, wherein " R " touches the plate agent for being present in organic in the intracrystalline hole system, and " m " is every mole of (Si xAl yP z) O 2" R " molal quantity that exists, its numerical value is 0～0.3, " x ", " y ", " z " are respectively the molar fraction of silicon, aluminium and phosphorus, and satisfy x+y+z=1.Typical SAPO molecular sieve is SAPO-17, SAPO-18, SAPO-34, SAPO-44 etc., and wherein, the SAPO-34 molecular sieve is 8 membered ring channels with CHA structure, and the hole is 3.8 * 3.8 dusts.At CN1096496A, USP4, the method for synthetic this molecular sieve is disclosed in 440,871 documents such as grade.
Metal-modified SAPO-34 molecular sieve provided by the invention, normally with the water soluble salt of metallic element, as ferric sulfate, ferrous sulfate, ferric nitrate, iron chloride, frerrous chloride, cobaltous sulfate, cobalt nitrate, cobalt chloride, nickelous sulfate, nickel nitrate or nickel chloride etc., according to the amount of on molecular sieve, intending load, they are dissolved in the solution of being made up of the water of the ethanol of 0～90 heavy % and 10～100 heavy % make maceration extract, according to the equivalent impregnation method of routine zeolite is flooded in maceration extract again, dry back obtained 400～800 ℃ of following calcination process in 0.5～8 hour, and wherein said calcination process process also can be to carry out under steam atmosphere.
Metal-modified SAPO-34 molecular sieve provided by the invention has better in the petroleum hydrocarbon cracking process, increases the performance of propylene content.For example, in base catalyst: the weight ratio of molecular sieve=95: 5,500 ℃ of reaction temperatures, 600 ℃ of regeneration temperatures, oil ratio 2.94, under the catalytic cracking fixed bed micro anti-evaluation condition of catalyst inventory 5 gram, adopt molecular sieve provided by the invention to change under the little situation of little, coke, dry gas amplification C at conversion ratio 3 =/ total C 3Than being 0.70～0.75, density of propylene is 41.61～43.08 in the liquefied gas, productivity of propylene is 12.75～13.79, and liquefied gas yield is 30.64～32.01, and the respective value of Comparative Examples is 0.35～0.60,35.61～37.04,7.66～11.03,21.51～29.78.
Metal-modified SAPO-34 molecular sieve provided by the invention can be applied in the cracking process of petroleum hydrocarbon as the active component of catalyst or auxiliary agent, and its content is approximately 1～50 heavy % in proportion in catalyst or auxiliary agent.
The specific embodiment
Following example will the present invention is further illustrated, but not thereby limiting the invention.
In each example and Comparative Examples, Fe in the products molecule sieve 2O 3, Co 2O 3, Ni 2O 3, Al 2O 3, SiO 2And P 2O 5Content measure (referring to " petrochemical industry analytical method (RIPP experimental technique) ", volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with x-ray fluorescence method.
Comparative Examples 1
This Comparative Examples prepares the SAPO-34 molecular sieve according to the process that provides among the CN1096496A.
In 250 gram deionized waters, add 105.6 grams and contain H 3PO 4The orthophosphoric acid solution of 85wt% and 58.8 grams contain Al 2O 372.18 the pseudobochmite powder of heavy %, be stirred well to evenly after, add 49.5 grams successively and contain SiO 2The Ludox of 40 heavy %, 118 gram deionized waters and 72 gram diethylamine.Fully stir and make gel, dress is enclosed to be had in the teflon-lined stainless steel autoclave, wears out 24 hours at 100 ℃, again 200 ℃ of reactions 72 hours.Filter out solid product then, after washing, drying, removed organic amine in 4 hours in 550 ℃ of roastings and obtain molecular sieve, its elementary analytical chemistry consists of: 19.8Al 2O 353.6P 2O 526.6SiO 2
Comparative Examples 2
According to the MFI structure molecular screen of CN1465527A preparation with phosphorus-iron modification.
With 20gNH 4Cl is dissolved in the 1000g water, and (the Chang Ling catalyst plant is produced, and non-amine method is synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution 2/ Al 2O 3=30), 90 ℃ the exchange 0.5h after, filter filter cake; Add 3.2gH 3PO 4(concentration 85%) and 8.7gFe (NO 3) 39H 2O is dissolved in the 90g water, dries with the filter cake hybrid infusion; The gained sample was 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.1Na 2O4.8Al 2O 32.0P 2O 51.7Fe 2O 391.4SiO 2
Example 1
With 6.6gFe (NO 3) 39H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A, the gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 1.3Fe 2O 320.1Al 2O 352.2P 2O 526.4SiO 2
Example 2
With 3.1gFeCl 3Be dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A, the gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 1.5Fe 2O 36.5Al 2O 344.7P 2O 547.3SiO 2
Example 3
With 4.6gFeSO 46H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 1.4Fe 2O 348.1Al 2O 345.2P 2O 55.3SiO 2
Example 4
With 7.4gCo (NO 3) 26H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 2.0Co 2O 319.9Al 2O 351.9P 2O 526.2SiO 2
Example 5
With 6.7gNi (NO 3) 26H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 1.8Ni 2O 319.6Al 2O 352.3P 2O 526.3SiO 2
Example 6
With 2.6gFe (NO 3) 39H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 0.5Fe 2O 317.2Al 2O 367.8P 2O 514.5SiO 2
Example 7
With 28.3gFe (NO 3) 39H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 5.2Fe 2O 338.7Al 2O 310.5P 2O 545.6SiO 2
Example 8
With 57.9gFe (NO 3) 39H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 10.1Fe 2O 317.7Al 2O 348.2P 2O 524SiO 2
Example 9
With 5.9gFe (NO 3) 39H 2O and 3.8gCo (NO 3) 26H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 1.0Fe 2O 31.1Co 2O 318.7Al 2O 349.3P 2O 529.9SiO 2
Example 10
With 5.9gFe (NO 3) 39H 2O and 6.0gNi (NO 3) 26H 2O is dissolved in the mixed solution of 90g water and 10g ethanol, with the SAPO-34 molecular sieve hybrid infusion oven dry of 100g (butt) according to the process preparation that provides among the CN1096496A; The gained sample obtains molecular sieve 550 ℃ of calcination process 2 hours, and its elementary analytical chemistry consists of: 1.1Fe 2O 31.4Ni 2O 319.6Al 2O 345.4P 2O 532.5SiO 2
Example 11
This example illustrates the effect of molecular sieve provided by the invention in pure hydrocarbon catalytic cracking probe reaction.
The sample that above-mentioned example and Comparative Examples are made carries out 800 ℃, 100% steam respectively on the fixed bed aging equipment handled in aging 4 hours, and compressing tablet sieves out 20-40 purpose particle, on the pure hydrocarbon micro-reactor of fixed bed, estimate, cracked stock is a hexane, appreciation condition is inlet amount 1g, 600 ℃ of reaction temperatures, catalyst inventory 1g.Evaluation result is listed in table 1.
Table 1
Example number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Examples 1 Comparative Examples 2
H2，w％ 6.41 5.27 5.67 5.48 5.81 5.43 6.13 5.77 5.87 5.75 5.58 5.64
CH4，w％ 14.10 13.19 15.84 13.82 12.87 13.09 14.02 13.76 13.94 13.90 5.85 12.84
C2H6，w％ 8.33 9.23 8.04 8.75 8.92 9.14 8.46 8.66 8.58 8.63 10.13 8.67
C2H4，w％ 17.31 16.04 18.91 16.95 16.10 16.06 17.20 16.94 17.10 17.06 10.92 16.51
C3H8，w％ 10.90 13.63 10.64 14.13 14.75 13.97 11.87 13.52 12.77 13.18 37.13 18.59
C3H6，w％ 33.65 33.63 33.57 32.11 31.78 33.08 33.19 32.32 32.76 32.56 15.01 28.00
IC4H10，w％ 1.28 1.32 0.95 1.37 1.57 1.40 1.31 1.38 1.33 1.34 4.01 1.87
NC4H10，w％ 2.24 2.42 2.13 2.54 2.66 2.49 2.33 2.50 2.41 2.45 5.63 3.18
C4＝，w％ 1.60 1.32 1.18 1.24 1.42 1.35 1.49 1.35 1.39 1.35 1.08 1.15
IC4＝，w％ 1.28 1.54 0.95 1.34 1.52 1.53 1.30 1.35 1.32 1.32 2.49 1.41
Anti-C4=, w% 1.60 1.32 1.18 1.25 1.44 1.36 1.50 1.36 1.40 1.36 1.22 1.19
Along C4=, w% 1.28 1.10 0.95 1.02 1.17 1.12 1.20 1.10 1.13 1.10 0.95 0.95
C3＝/∑C3 0.76 0.71 0.76 0.69 0.68 0.70 0.74 0.70 0.72 0.71 0.29 0.60
C2＝/∑C2 0.68 0.63 0.70 0.66 0.64 0.63 0.67 0.66 0.67 0.66 0.52 0.66
C2＝+C3＝ 50.96 49.67 52.48 49.06 47.88 49.13 50.39 49.26 49.86 49.62 25.93 44.52
C3＝/C2＝ 1.94 2.10 1.78 1.89 1.97 2.06 1.93 1.91 1.91 1.91 1.37 1.70
C3＝/C4＝ 5.83 6.38 7.89 6.62 5.73 6.19 6.07 6.38 6.29 6.39 2.61 5.95
As can be seen from Table 1, use metal-modified SAPO-34 molecular sieve provided by the invention in the hexane cracking reaction, compare with 2 result with Comparative Examples 1, under the constant substantially situation of hydrogen, selectivity of light olefin significantly increases, C 3 =/ ∑ C 3Ratio significantly improves.
Example 12
The explanation of this example adopts molecular sieve provided by the invention to be used for catalytic cracking of petroleum hydrocarbon, for C 2-C 4The productive rate of alkene and optionally influence.
The sample that above-mentioned example and Comparative Examples are made carries out 800 ℃, 100% steam respectively on the fixed bed aging equipment handled in aging 4 hours, and compressing tablet sieves out 20-40 purpose particle, use the industrial poising agent of catalyst DOCP (production of Chang Ling catalyst plant) to make base catalyst then, mix by 95: 5 weight ratio with each molecular sieve respectively and convert evenly, estimate on anti-in that the catalytic cracking fixed bed is little again, appreciation condition is 500 ℃ of reaction temperatures, 600 ℃ of regeneration temperatures, oil ratio 2.94, catalyst inventory 5 grams.
Feedstock oil character sees Table 2.Evaluation result is listed in table 3.
Table 2
Project Analyze data
Density (20 ℃)/g/cm 3Refractive power (70 ℃) viscosity (80 ℃)/mm 2/ s vacuum distillation range/℃ initial boiling point 5% 10% 30% 50% 70% 90% acid number/mgKOH/g carbon residue/% ash content/% S content/% N content/% C, H content/% C H 0.8731 1.4682 17.56 189 398 418 457 497 549 73.5％，560℃ 0.07 0.7 0.05 0.12 0.11 86.43 13.53
Table 3
Example number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Examples 1 Comparative Examples 2
Material balance/m%
Dry gas 2.02 2.01 1.95 1.90 1.95 1.99 1.98 1.97 1.95 1.94 1.84 1.96
Liquefied gas 31.38 31.25 32.01 31.03 30.64 31.07 31.28 30.82 31.18 31.15 21.51 29.78
Gasoline 42.35 43.01 43.56 44.86 44.07 43.33 43.10 43.75 43.80 44.02 51.44 45.01
Diesel oil 12.11 11.90 10.19 9.64 10.79 11.57 11.37 11.12 10.68 10.47 11.54 11.51
Heavy oil 9.28 9.15 9.71 9.62 9.55 9.27 9.38 9.43 9.48 9.50 10.95 9.02
Coke 2.86 2.68 2.58 2.95 3.00 2.78 2.89 2.90 2.91 2.92 2.72 2.72
Conversion ratio/m% 78.61 78.95 80.10 80.74 79.66 79.16 79.25 79.45 79.85 80.02 77.51 79.47
Propylene, m% 13.34 13.22 13.79 12.96 12.75 13.08 13.23 12.89 13.12 13.09 7.66 11.03
Density of propylene in the liquefied gas, % 42.51 42.30 43.08 41.77 41.61 42.09 42.29 41.82 42.08 42.02 35.61 37.04
Total butylene, m% 10.43 10.12 10.77 10.03 9.98 10.08 10.31 10.02 10.20 10.16 6.73 9.32
C 2 ＝/ total C 2 0.74 0.73 0.74 0.70 0.73 0.73 0.73 0.73 0.72 0.71 0.63 0.71
C 3 ＝/ total C 3 0.75 0.77 0.74 0.71 0.70 0.75 0.74 0.72 0.73 0.72 0.35 0.60
As can be seen from Table 3, in catalytic cracking catalyst, add metal-modified SAPO-34 molecular sieve provided by the invention after, compare with the result of Comparative Examples, change under the little situation of little, coke, dry gas amplification C at conversion ratio 3 =/ total C 3Than improving, density of propylene improves in the liquefied gas, and productivity of propylene and selectivity improve, and higher liquefied gas yield.

Claims (6)

1. metal-modified SAPO-34 molecular sieve is characterized in that the anhydrous chemical expression of this molecular sieve, counts (0.1～15) M with the quality of oxide xO y(0.9～72) Al 2O 3(1～78) P 2O 5(0.4～97) SiO 2Wherein, M is selected from transition metal Fe, among Co and the Ni one or both, x represents the atomicity of M, y represents to satisfy the required number of M oxidation state, metal-modified process is the water soluble salt with transition metal, according to the amount of on the SAPO-34 molecular sieve, intending load, they are dissolved in the solution of being made up of the water of the ethanol of 0～90 weight % and 10～100 weight % make maceration extract, according to the equivalent impregnation method of routine the SAPO-34 molecular sieve is flooded in maceration extract, dry back obtained metal-modified SAPO-34 molecular sieve in 0.5～8 hour 400～800 ℃ of following calcination process again.
2. according to the molecular sieve of claim 1, it is characterized in that anhydrous chemical expression, count (0.5～10) M with the quality of oxide xO y(5～50) Al 2O 3(10～70) P 2O 5(5～50) SiO 2
3. according to the molecular sieve of claim 1 or 2, said transition metal is Fe.
4. according to the molecular sieve of claim 1 or 2, said transition metal is Fe and Co.
5. according to the molecular sieve of claim 1 or 2, said transition metal is Fe and Ni.
6. claim 1 or 2 molecular sieve are applied in the cracking process of petroleum hydrocarbon as the active component of catalyst or auxiliary agent, and its content is counted 1～50 weight % with proportion in catalyst or auxiliary agent.
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Publication number Priority date Publication date Assignee Title
US9802182B2 (en) 2013-03-13 2017-10-31 Basf Corporation Stabilized metal-exchanged SAPO material
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