CN1176020C - MFI structure molecular sieve containing phosphorus and transition metal - Google Patents

MFI structure molecular sieve containing phosphorus and transition metal Download PDF

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CN1176020C
CN1176020C CNB021215863A CN02121586A CN1176020C CN 1176020 C CN1176020 C CN 1176020C CN B021215863 A CNB021215863 A CN B021215863A CN 02121586 A CN02121586 A CN 02121586A CN 1176020 C CN1176020 C CN 1176020C
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molecular sieve
mfi structure
transition metal
water
zsm
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CN1465527A (en
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罗一斌
李明罡
舒兴田
何鸣元
田素贤
宗保宁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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

A kind of MFI structure molecular screen of phosphorous and transition metal
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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