CN1176020C - MFI structure molecular sieve containing phosphorus and transition metal - Google Patents
MFI structure molecular sieve containing phosphorus and transition metal Download PDFInfo
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Abstract
The present invention discloses an MFI structure molecular sieve containing phosphorus and transition metal, which is characterized in that the molecular sieve has an anhydrous chemical expression measured by the oxide mass: (0 to 0.3) Na2O /(0.5 to 5) Al2O3 /(1.3 to 10) P2O5 /(0.7 to 15) M2O3 /(70 to 99) SiO2, wherein M is selected from one of the transition metal elements of Fe, Co and Ni. The molecular sieve is applied to the catalytic cracking process of petroleum hydrocarbons. Compared with the molecular sieve provided by the prior art, the present invention can improve the productivity and the selectivity of C2 to C4 olefinic hydrocarbon and have high productivity of liquid gas.
Description
Technical field
The invention relates to a kind of MFI structure molecular screen and preparation method thereof, the MFI structure molecular screen about a kind of phosphorous and transition metal and preparation method thereof of further saying so.
Technical background
Typical case's representative with molecular sieve of MFI structure is the ZSM-5 zeolite of early seventies U.S. Mobil company exploitation, and it has unique pore passage structure, is widely used in the reaction process such as alkylation, isomerization, disproportionation, catalytic cracking, catalytic dewaxing.Catalytic cracking is to produce one of important production technique of light olefin, and for most of catalytic cracking unit, for propylene enhancing and butylene output, it is effective means that employing contains catalyzer or auxiliary agent with MFI structure molecular screen.
At USP 3,758, in 403, disclosed the method for in catalytic cracking catalyst, adding the ZSM-5 molecular sieve and can improve the octane value of gasoline and increase C
3-C
4The productive rate of alkene.For example in containing the conventional catalyst of 10%REY, add from 1.5,2.5, behind 5 to 10% the ZSM-5 molecular sieve, the gain in yield of gasoline octane rating and low-carbon alkene, but with the increase of ZSM-5 molecular sieve amount, the amplitude of this increase reduces.Use has same effect when containing the auxiliary agent of ZSM-5 molecular sieve.
USP5,318,696 have proposed the hydrocarbon conversion process process of the catalyzer formed less than 30 the molecular sieve with MFI structure based on a kind of large pore molecular sieve and silica alumina ratio.This technology is produced stop bracket gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
USP5997728 discloses a large amount of methods of using the shape slective cracking auxiliary agent in the heavy feed stock catalytic cracking process.Auxiliary agent is made up of the ZSM-5 molecular sieve that adds 12-40% in the [amorphous, and system's reserve at least 10% makes the ratio of ZSM-5 in catalyzer surpass 3%.This method can additionally not increase aromatic production and loss gasoline yield when significantly improving low-carbon alkene.
CN1034223A discloses a kind of catalyst for cracking that is used to produce low-carbon alkene, is made up of the clay of 0～70% (is benchmark in the catalyst weight), 5～99% inorganic oxide and 1～50% zeolite.Zeolite wherein is the mixture of the five-ring supersiliceous zeolite of the REY of 0～25 heavy % or the phosphorous and rare earth that type-Y high silicon zeolite and 75～100 weighs %.It is higher hydro-thermal activity stability, transformation efficiency and the C of catalyzer of active ingredient with the HZSM-5 zeolite that this catalyzer has
2 -～C
4 -Productive rate.
CN1147420A discloses a kind of phosphorous and rare earth and has had the molecular sieve of MFI structure, and its anhydrous chemical constitution is aRE
2O
3BNa
2OAl
2O
3CP
2O
5DSiO
2, a=0.01-0.25 wherein, b=0.005-0.02, c=0.2-1.0, d=35-120.This molecular sieve has excellent hydrothermal activity stability and good selectivity of light olefin when being used for the hydro carbons pyrolytic conversion.
After the ZSM-5 molecular sieve carried out modification with P contained compound, its cracking activity stability can improve, and reduced the consumption of molecular sieve.
In USP5110776, the preparation method with the ZSM-5 molecular sieve catalyst of phosphorus modification is disclosed.Said phosphorus modifying process is that molecular sieve is dispersed in the P contained compound aqueous solution of pH value 2-6, then with matrix making beating, spray drying forming.The gained catalyzer does not increase dry gas and coke yield when improving gasoline octane rating.
USP5171921 discloses a kind of ZSM-5 molecular sieve with the phosphorus modification.This molecular sieve has the silica alumina ratio of 20-60, with P contained compound dipping after after 500～700 ℃ of steam treatment, be used for C
3-C
20Hydrocarbon changes into C
2-C
5During the reaction of alkene, the HZSM-5 that handles without phosphorus has higher activity relatively.
Molecular sieve has following relevant report with metal-modified method and application thereof, for example USP5236880 discloses the catalyzer that comprises MFI or MEL structure molecular screen, the catalyzer that has added modified molecular screen is used for can increasing octane value, the aromaticity content of C5-C12 gasoline when alkane transforms and/or improving gasoline yield, the catalyzer that contains the molecular sieve of modification like this can improve the octane value of gasoline, increases C
3～C
4The productive rate of alkene.Used molecular sieve is through VIII family metal, preferably with the Ni modification.After this molecular sieve was introduced Ni, heat or hydrothermal treatment consists under the controlled temperature of experience harshness made VIII family metal and aluminium at surface enrichment.
CN1057408A discloses a kind of catalyst for cracking that contains supersiliceous zeolite, has higher catalytic pyrolysis activity, wherein said supersiliceous zeolite is ZSM-5, β zeolite or the mordenite that contains 0.01～3.0 heavy % phosphorus, 0.01～1.0 heavy % iron or 0.01～10 heavy % aluminium, be that silica alumina ratio is heated to 350-820 ℃ greater than 15 Hydrogen or potassium type ZSM molecular sieve, β zeolite or mordenite, with 0.1-10 hour ↑
[1]Volume space velocity feed and to obtain behind the halide solution of halide solution, iron of aluminium or the saline solution of ammonium phosphate.
Summary of the invention
Along with the development of petrochemical industry, the demand of low-carbon alkene raw material is day by day enlarged, therefore, the purpose of this invention is to provide a kind of molecular sieve of MFI structure, this molecular sieve as FCC catalyzer or auxiliary agent select the shape active component, can improve C
2～C
4Olefins yield and selectivity.
The molecular sieve of MFI structure provided by the present invention, its anhydrous chemical expression is counted with the weight of oxide compound: (0～0.3) Na
2O (0.5～6) Al
2O
3(1.3～10) P
2O
5(0.7～15) M
2O
3(70～99) SiO
2, wherein, M is selected from a kind of among Fe, Co or the Ni, preferred Fe.
The said MFI molecular sieve of the present invention, preferred ZSM-5, its anhydrous chemical expression in the preferable range of the weight of oxide compound is: (0～0.2) Na
2O (0.9～5.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
2O
3(82～92) SiO
2
MFI structure molecular screen provided by the present invention, its preparation process comprise ammonia exchange, phosphorus modification, metal-modified and calcination process step, say so more specifically the sodium type molecular sieve with MFI structure of conventional crystallization gained according to molecular sieve: ammonia salt: H
2O=1: (0.1～1): the weight ratio of (5～10) is at room temperature to 100 ℃ 0.3～1 hour after-filtration of following exchange, introduce phosphorus and be selected from a kind of among Fe, Co or the Ni molecular sieve is carried out modification, 400～800 ℃ of following calcination process 0.5～8 hour, wherein said calcination process process also can be roasting under steam atmosphere.
MFI structure molecular screen provided by the present invention, said sodium type molecular sieve in preparation process with MFI structure, if adopt organic formwork agent synthetic words, should behind removed template method, carry out operation as above again, wherein said ammonium salt can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture for inorganic ammonium salt commonly used.
MFI structure molecular screen provided by the present invention, said phosphorus and be selected from a kind of among Fe, Co or the Ni molecular sieve is carried out modification can be to adopt the mode of dipping or ion-exchange to carry out in preparation process.
Wherein said dipping can adopt following three kinds of modes again:
A. the P contained compound aqueous solution of filter cake after the ammonia exchange and calculated amount is evenly dried in room temperature to 95 a ℃ making beating, after roasting under 400～800 ℃ of conditions, ℃ mix, dry in room temperature to 95 with the compound water solution that contains one of Fe, Co or Ni of calculated amount again.
B. the P contained compound aqueous solution of filter cake after the ammonia exchange and calculated amount is evenly dried in room temperature to 95 a ℃ making beating, ℃ mix oven dry with the compound water solution that contains one of Fe, Co or Ni of calculated amount in room temperature to 95 again, wherein reversed order that also can the above-mentioned two kinds of solution of dipping.
C. the mixed aqueous solution of the P contained compound of the filter cake after the ammonia exchange and calculated amount and the compound of one of Fe, Co or Ni ℃ is mixed afterwards in room temperature to 95 and dry.
Said ion-exchange is: the P contained compound aqueous solution of filter cake after the ammonia exchange and calculated amount is evenly dried in room temperature to 95 a ℃ making beating, after roasting under 400～800 ℃ of conditions, again with the compound water solution that contains one of Fe, Co or Ni of calculated amount by 1: after the solid-to-liquid ratio of (5～20) mixes, at 80～95 ℃, pH=4～7 time 2～3 hours after-filtration of stirring, but repeated exchanged repeatedly, and exchange back gained samples with water is washed repeatedly, and oven dry gets final product.
MFI structure molecular screen provided by the present invention, said P contained compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate or its mixture in preparation process.
MFI structure molecular screen provided by the present invention, said Fe, Co or Ni compound are selected from their water-soluble salt in preparation process, and said water-soluble salt is selected from a kind of in ferric sulfate, ferrous sulfate, iron nitrate, iron(ic) chloride, iron protochloride, rose vitriol, Xiao Suangu, cobalt chloride, single nickel salt, nickelous nitrate or the nickelous chloride.
MFI structure molecular screen provided by the present invention, contain phosphorus and transition metal, combine closely in the dehydrogenation center of its acid site and transition metal, and the existence of phosphorus simultaneously not only can improve the structural stability of molecular sieve but also the dehydrogenation ability of transition metal is partly poisoned, synergy by the different activities center, can make this molecular sieve in the catalytic cracking process of petroleum hydrocarbon than prior art, have higher liquefied gas yield, especially to C
2～C
4The productive rate and the selectivity of alkene further improve, and dry gas amplification is less simultaneously.
Embodiment
Following example will the present invention is further illustrated, but not thereby limiting the invention.
In each example and Comparative Examples, Na in the products molecule sieve
2O, Fe
2O
3, Co
2O
3, Ni
2O
3, Al
2O
3, SiO
2Content measure (referring to " petrochemical complex analytical procedure (RIPP experimental technique) ", volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with x-ray fluorescence method.
Example 1
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 2.4gFe (NO
3)
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; The gained sample is at 550 ℃ of calcination process 2 hours, molecular sieve promptly provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O5.0Al
2O
32.0P
2O
50.9Fe
2O
392SiO
2
Example 2
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 2.4gH
3PO
4(concentration 85%) and 2.3gFeCl
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; The gained sample is at 550 ℃ of calcination process 2 hours, molecular sieve promptly provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O5.3Al
2O
31.5P
2O
51.1Fe
2O
392SiO
2
Example 3
With 50gNH
4Cl is dissolved in the 1000g water, and (the Chang Ling catalyst plant is produced, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=70), 85 ℃ the exchange 0.5h after, filter filter cake; With 8.0gNH
4H
2PO
4Be dissolved in the 60g water, with filter cake hybrid infusion oven dry, through 550 ℃ of calcination process 2 hours; An a 0 5% Fe (NO with above-mentioned sample in 5: 1 ratio of solid-to-liquid ratio and concentration
3)
3Solution filters 80～90 ℃ of down exchanges 2 hours, exchanges several times again, until reaching aim parameter, and again 550 ℃ of calcination process 2 hours, molecular sieve promptly provided by the invention.Elementary analytical chemistry consists of 0.03Na
2O2.2Al
2O
34.9P
2O
52.1Fe
2O
390.8SiO
2
Example 4
With 80gNH
4Cl is dissolved in the 1000g water, and (the Chang Ling catalyst plant is produced, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=170), 85 ℃ the exchange 0.5h after, filter filter cake; With 8.9gNH
4H
2PO
4Be dissolved in the 60g water, with filter cake hybrid infusion, oven dry; With 31.9gFeSO
46H
2O is dissolved in the 90g water, with above-mentioned sample mix dipping, oven dry, and again 600 ℃ of calcination process 2 hours, molecular sieve promptly provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O0.94Al
2O
35.1P
2O
510.1Fe
2O
384SiO
2
Example 5
With 50g (NH
4)
2SO
4Be dissolved in the 1000g water, (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), 85 ℃ the exchange 0.5h after, filter filter cake; With 7.8gNH
4H
2PO
4Be dissolved in the 60g water, dry with the filter cake hybrid infusion; With 13.9gCo (NO
3)
26H
2O is dissolved in the 90g water, with the oven dry of above-mentioned sample mix dipping; The gained sample is molecular sieve provided by the invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.03Na
2O5.1Al
2O
34.8P
2O
53.6Co
2O
386.5SiO
2
Example 6
With 80gNH
4NO
3Be dissolved in the 1000g water, (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), 85 ℃ the exchange 0.5h after, filter filter cake; With 13.0g (NH
4)
2HPO
4Be dissolved in the 60g water, dry with the filter cake hybrid infusion; Add 26.2gNiSO again
46H
2O is dissolved in the 90g water, with the oven dry of above-mentioned sample mix dipping; Products therefrom was 600 ℃ of calcination process 2 hours, and products therefrom is a molecular sieve provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O4.6Al
2O
36.9P
2O
56.4Ni
2O
382SiO
2
Example 7
With 80gNH
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), 85 ℃ the exchange 0.5h after, filter filter cake; With 8.6g (NH
4)
2HPO
4Be dissolved in the 60g water, dry with the filter cake hybrid infusion; Add 7.5gNi (NO again
3)
26H
2O is dissolved in the 90g water, with the oven dry of above-mentioned sample mix dipping; The gained sample was 600 ℃ of calcination process 2 hours, and products therefrom is a molecular sieve provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O5.2Al
2O
34.5P
2O
52.0Ni
2O
388.2SiO
2
Comparative Examples 1
Prepare phosphorous and rare earth and have the molecular sieve of MFI structure by the method for CN1147420.
The 150gREY crystal seed is dispersed in 11.3 kilograms contains 3.5%Na
2O and 11%SiO
2Water glass in, stir and to add 1300g down and contain 2.5%Al
2O
3Alum liquor, the sulfuric acid with 20% makes it to form gel with system Ph value to 11.5.This gel filters 180 ℃ of following crystallization 16 hours, and washing obtains crystallization product.Get above-mentioned crystallization product 1000g, add 8% ammonium sulfate solution 6250g, stir following 60 ℃ of exchanges 1 hour, filter, washing gets ammonium type crystallization product.Get ammonium type crystallization product 100g, add 0.5% fluorine silicic acid aqueous solution 1600g, stirred following 50 ℃ of dealumination reactions 5 hours.
In above-mentioned dealuminzation product, add by what pseudo-boehmite and phosphoric acid were formed and contain 4.4%Al
2O
3Phosphorus aluminium activator 8.4g and 40g water, it is mixed, 120 ℃ of dryings 4 hours, 600 ℃ of steam atmospheres are reaction 1.5h down, the molecular sieve of phosphorous and rare earth.The anhydrous chemical constitution of this molecular sieve is 1.5RE
2O
30.03Na
2O4.1Al
2O
31.5P
2O
592SiO
2
Comparative Examples 2
According to USP5,472, the 594 preparations ZSM-5 molecular sieve of phosphorus modification.
With 20gNH
4Cl is dissolved in the 1000g water, and (the Chang Ling catalyst plant is produced, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=70), 90 ℃ the exchange 0.5h after, filter filter cake; Add 3.4gH
3PO
4(concentration 85%) stirs 0.5h under the room temperature, oven dry; Products therefrom is at 500 ℃ of calcination process 1 hour, molecular sieve promptly provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O2.4Al
2O
32.1P
2O
596.4SiO
2
Comparative Examples 3
This Comparative Examples is the described molecular sieve of preparation CN1058407A.
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 1.7gH
3PO
4(concentration 85%) and 1.3gFeCl
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; The gained sample is at 550 ℃ of calcination process 2 hours, molecular sieve promptly provided by the invention.Elementary analytical chemistry consists of 0.1Na
2O5.4Al
2O
31.0P
2O
50.5Fe
2O
392SiO
2
Example 8
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 poiser of catalyzer 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 temperature of reaction, 600 ℃ of regeneration temperatures, agent-oil ratio 2.94, catalyst inventory 5g.Stock oil character sees Table 1.Evaluation result is listed in table 2.
Table 1
The project analysis data
Density (20 ℃)/g/cm
30.8731
Refractive power (70 ℃) 1.4682
Viscosity (80 ℃)/mm
2/ s 17.56
Vacuum distillation range/℃
Initial boiling point 189
5％ 398
10％ 418
30％ 457
50％ 497
70％ 549
90％ 73.5％，560℃
Acid number/mgKOH/g 0.07
Carbon residue/% 0.7
Ash content/% 0.05
S content/% 0.12
N content/% 0.11
C, H content/%
C 86.43
H 13.53
Table 2
| Example number | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Material balance/m% | ||||||||||
| Dry gas | 1.87 | 2.01 | 2.07 | 2.10 | 1.95 | 2.44 | 2.27 | 1.38 | 1.34 | 1.54 |
| Liquefied gas | 29.81 | 31.23 | 31.59 | 31.38 | 29.64 | 29.30 | 26.09 | 23.26 | 21.51 | 24.9 |
| Gasoline | 45.18 | 43.31 | 44.58 | 42.38 | 43.47 | 40.35 | 44.56 | 51.14 | 50.44 | 49.2 |
| Diesel oil | 11.63 | 11.69 | 11.27 | 11.76 | 12.30 | 12.77 | 13.84 | 12.94 | 13.06 | 12.4 |
| Heavy oil | 8.79 | 9.14 | 7.71 | 9.31 | 9.54 | 12.08 | 10.55 | 8.66 | 10.95 | 9.10 |
| Coke | 2.72 | 2.71 | 2.98 | 3.06 | 3.00 | 3.07 | 2.69 | 2.62 | 2.72 | 2.86 |
| Transformation efficiency/m% | 79.58 | 79.26 | 81.63 | 78.92 | 78.16 | 75.15 | 75.61 | 78.4 | 75.99 | 78.5 |
| C2 ＝/ total C2 | 0.71 | 0.73 | 0.74 | 0.74 | 0.73 | 0.74 | 0.76 | 0.6 | 0.63 | 0.61 |
| Propylene, m% | 11.03 | 11.22 | 11.79 | 11.34 | 9.95 | 10.22 | 9.21 | 8.16 | 7.66 | 8.90 |
| Total butylene, m% | 9.32 | 10.11 | 9.77 | 10.41 | 9.38 | 10.84 | 9.10 | 7.99 | 6.73 | 8.10 |
| Iso-butylene, m% | 3.49 | 3.77 | 3.69 | 3.58 | 3.58 | 4.00 | 3.38 | 2.65 | 2.32 | 2.73 |
As can be seen from Table 2, in catalytic cracking catalyst, add MFI 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 transformation efficiency
2 =/ total C2 is than improving, and propylene and butylene particularly selective isobutene improve, and higher liquefied gas yield.
Claims (4)
1, a kind of MFI structure molecular screen of phosphorous and transition metal is characterized in that the anhydrous chemical expression of this molecular sieve, counts (0～0.3) Na with the quality of oxide compound
2O (0.5～6) Al
2O
3(1.3～10) P
2O
5(0.7～15) M
2O
3(70～92) SiO
2, wherein, M is selected from a kind of among transition metal Fe, Co and the Ni.
2,, it is characterized in that M is Fe according to the described MFI structure molecular screen of claim 1.
3,, it is characterized in that said MFI structure molecular screen is the ZSM-5 molecular sieve according to the described MFI structure molecular screen of claim 1.
4, according to the described MFI structure molecular screen of claim 1, it is characterized in that the anhydrous chemical expression of this molecular sieve, count (0～0.2) Na with the quality of oxide compound
2O (0.9～5.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
2O
3(82～92) SiO
2
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2002
- 2002-06-27 CN CNB021215863A patent/CN1176020C/en not_active Expired - Lifetime
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| CN101213269B (en) * | 2005-06-29 | 2012-01-25 | 格雷斯公司 | Five-membered ring silicalite catalysts for light olefins in fluidized catalytic units |
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| CN103007986B (en) * | 2011-09-22 | 2014-12-31 | 中国石油化工股份有限公司 | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration |
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