CN102452669B - MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method - Google Patents
MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method Download PDFInfo
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- CN102452669B CN102452669B CN 201010515404 CN201010515404A CN102452669B CN 102452669 B CN102452669 B CN 102452669B CN 201010515404 CN201010515404 CN 201010515404 CN 201010515404 A CN201010515404 A CN 201010515404A CN 102452669 B CN102452669 B CN 102452669B
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Abstract
The invention relates to a MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method. The anhydrous chemical expression of the molecular sieve is (0-0.3) Na2O.(0.5-6) Al2O3.(1.3-10) P2O5.(0.7-15) MxOy.(70-97) SiO2, wherein M is selected from one or more of Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi, x is expressed as atomicity of M, y is expressed as a number which satisfies the requirement of an oxidation state of M; No characteristic absorption peak is existed at 1633cm<-1> on infrared spectrum by molecular sieve trimethylpyridine adsorption. The preparation method comprises that phosphor and transition metal are introduced in molecular sieve with the MFI structure during ammonium exchanging, wherein the phosphor introduction is divided into two parts, a part of phosphor is introduced before introducing the transition metal or at the same time with transition metal introduction, the other part of the phosphor is introduced after the transition metal introduction. The provided molecular sieve is used for conversing hydrocarbon oil, the yield of dry gas and coke is low, and the yield of propylene and isobutene is high.
Description
Technical field
The present invention relates to MFI structure molecular screen of a kind of phosphorous and transition metal and preparation method thereof.
Background technology
Typical 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, it is effective means that employing contains catalyzer or auxiliary agent with MFI structure molecular screen.
USP 3,758, and 403 have disclosed in catalytic cracking catalyst and to add ZSM-5 molecular sieve as the method for active component.This method 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 behind 1.5%, 2.5%, 5% to 10% ZSM-5 molecular sieve, the corresponding increase of the productive rate of gasoline octane rating and low-carbon alkene, but with the increase of ZSM-5 molecular sieve add-on, the amplitude that gasoline octane rating and productivity of low carbon olefin hydrocarbon increase reduces.Use has same effect when containing the auxiliary agent of ZSM-5 molecular sieve.
USP 5,318, and 696 have proposed the hydrocarbon conversion process process of the catalyzer that forms less than 30 the molecular sieve with MFI structure based on a kind of large pore molecular sieve and silica alumina ratio.This technique is produced stop bracket gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
USP 5,997, and 728 disclose a large amount of methods of using the shape slective cracking auxiliary agent in the heavy feed stock catalytic cracking process.Described auxiliary agent is comprised of the ZSM-5 molecular sieve that adds 12～40% in the [amorphous, and system's reserve at least 10% is so that the ratio of ZSM-5 in catalyzer surpasses 3%.This method can when significantly improving low-carbon alkene, additionally not increase aromatic production and loss gasoline yield.
CN 1034223C discloses a kind of catalyst for cracking for the production of low-carbon alkene, is comprised of the clay of 0～70% (take catalyst weight as benchmark), 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 %.This catalyzer has hydrothermal activity stability, transformation efficiency and the C that the catalyzer take the HZSM-5 zeolite as active ingredient is higher
2 =～C
4 =Productive rate.
CN 1049406C discloses a kind of phosphorous and rare earth and has had the molecular sieve of MFI structure, and it is aRE without hydrochemical compositions
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 ZSM-5 molecular sieve carried out modification with P contained compound, its cracking activity stability can improve, and reduced the consumption of molecular sieve.
USP 5,110, and 776 disclose the preparation method take the ZSM-5 molecular sieve of phosphorus modification as the catalytic cracking catalyst of active component.Described 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.
USP 5,171, and 921 disclose a kind of ZSM-5 molecular sieve with the phosphorus modification.This molecular sieve has 20～60 silica alumina ratio, by after 500～700 ℃ of steam treatment, is used for C with the P contained compound dipping
3～C
20Hydrocarbon changes into C
2～C
5During the reaction of alkene, the HZSM-5 that relatively processes without phosphorus has higher activity.
Molecular sieve can have some special Catalytic Cracking Performances after metal-modified.
USP 5,236, and 880 disclose the catalyzer that comprises MFI or MEL structure molecular screen, and the catalyzer that has added above-mentioned modified molecular screen is used for can increasing C when alkane transforms
5～C
12The octane value of gasoline, aromaticity content and/or raising gasoline yield increase C
3～C
4The productive rate of alkene.Used molecular sieve is through VIII family metal, preferably make with the Ni modification.Molecular sieve carries out heat or hydrothermal treatment consists, so that VIII family metal and aluminium are at surface enrichment after introducing Ni under the control temperature of harshness.
CN 1037327C discloses a kind of catalyst for cracking that contains supersiliceous zeolite, it is active to have higher catalytic pyrolysis, 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, that silica alumina ratio is heated to 350-820 ℃ greater than 15 Hydrogen or potassium type ZSM molecular sieve, β zeolite or mordenite, with 0.1-10h
-1Volume space velocity pass into and obtain behind the halide solution of halide solution, iron of aluminium or the saline solution of ammonium phosphate.
CN 1176020C discloses a kind of phosphorus and transition metal modified MFI structure molecular screen, it is characterized in that the anhydrous chemical expression of this molecular sieve, counts (0～0.3) Na with the quality of oxide compound
2O (0.5～5) Al
2O
3(1.3～10) P
2O
5(0.7～15) M
2O
3(70～99) SiO
2Wherein, M is selected from a kind of among transition metal Fe, Co and the Ni.This molecular sieve is applied in the catalytic cracking process of petroleum hydrocarbon, compares with the molecular sieve that prior art provides, and can improve C
2～C
4The productive rate of alkene and selectivity have higher liquefied gas yield.
CN 1257796C discloses a kind of MFI structure molecular screen of phosphorous and metal component, and its anhydrous chemical expression is counted with the weight of oxide compound: (0～0.3) Na
2O (0.5～5.5) Al
2O
3(1.3～10) P
2O
5(0.7～15) M1
xO
y(0.01～5) M2
mO
n(70～97) SiO
2, wherein M1 is selected from a kind of among transition-metal Fe, Co and the Ni, and M2 is selected from any among Metal Zn, Mn, Ga and the Sn.
In the prior art, although can improve productivity of propylene and selectivity through phosphorus and transition metal modified MFI structure molecular screen for hydrocarbon oil catalytic cracking, dry gas and coke yield are higher.
Summary of the invention
The technical problem to be solved in the present invention is to be used for cracking hydrocarbon oil dry gas and the higher deficiency of coke yield for existing MFI structure molecular screen phosphorous and transition metal, and a kind of preparation method of MFI structure molecular screen of the phosphorous and transition metal that can reduce dry gas and coke yield is provided.The other technical problem that the present invention will solve provides a kind of modification MFI structure molecular screen of phosphorous and transition metal.
The invention provides a kind of preparation method of MFI structure molecular screen of phosphorous and transition metal, be included in the molecular sieve with MFI structure of ammonium exchange and introduce phosphorus and transition metal, described phosphorus divides two portions to introduce at least, part phosphorus is introduced after introducing transition metal, and a part of phosphorus is introduced before introducing transition metal or with transition metal simultaneously in addition; The MFI structure molecular screen of described phosphorous and transition metal, 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
xO
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably.
The present invention also provides a kind of MFI structure molecular screen of phosphorous and transition metal, and 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
xO
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi preferably; In the infrared spectrum that described molecular sieve obtains as probe with trimethylpyridine, at 1633cm
-1The place is without absorption peak.
Phosphorous and transition metal provided by the invention have a MFI structure molecular screen, in its trimethylpyridine absorption infrared spectrum at 1633cm
-1The place is without L acid charateristic avsorption band, and the L acid site of molecular sieve outer surface disappears substantially; Described molecular sieve is as the active ingredient of cracking catalyst or auxiliary agent, kept higher productivity of low carbon olefin hydrocarbon and selectivity, can not reduce productivity of low carbon olefin hydrocarbon and optionally reduce simultaneously dry gas and coke yield, the hydrogen yield decrease, be to improve yield of liquefied gas unexpectedly, significantly improve propylene and iso-butylene productive rate and selectivity.The MFI structure molecular screen preparation method of phosphorous and transition metal provided by the present invention, phosphorus is carried out load several times, the rich phosphorus of resulting molecular sieve outer surface, surperficial phosphorus content is higher than body phase phosphorus content, can obtain in the trimethylpyridine absorption infrared spectrum at 1633cm
-1The place is without the modified molecular screen of L acid charateristic avsorption band, prepared molecular sieve is active high, be used for hydrocarbon oil conversion, kept higher productivity of low carbon olefin hydrocarbon and selectivity, can not reduce productivity of low carbon olefin hydrocarbon and optionally reduce simultaneously dry gas and coke yield, the hydrogen yield decrease is to improve yield of liquefied gas unexpectedly, significantly improves propylene and iso-butylene productive rate and selectivity.
Description of drawings
Fig. 1 is the TEM-EDS spectrogram of the ZSM-5 molecular sieve of the phosphorus that obtains of the embodiment of the invention 1 and Comparative Examples 1 and iron modification.
Fig. 2 is the trimethylpyridine absorption infrared spectrum of the ZSM-5 molecular sieve of the phosphorus that obtains of the embodiment of the invention 1 and Comparative Examples 1 and iron modification modification, the spectrogram of the molecular sieve that figure center line 1 obtains for Comparative Examples 1, the infrared spectrum of the phosphorus that line 2 obtains for embodiment 1 and the ZSM-5 molecular sieve of iron modification modification.
Embodiment
The preparation method of the MFI structure molecular screen of phosphorous and transition metal provided by the present invention, in the molecular sieve with MFI structure of ammonium exchange, introduce phosphorus and transition metal, wherein phosphorus divides two portions to introduce, a part is that whole the introducing afterwards of transition metal introduced after transition metal is introduced, and introduces simultaneously before a part was introduced before the transition metal introducing is finished and namely introduced transition metal in addition or with transition metal.The phosphorus of introducing after described transition metal is introduced accounts for 10～90% of total phosphorus introducing amount in the molecular sieve, preferred 25～50%, described transition metal is introduced (introduce before the transition metal or with transition metal and introduce simultaneously) before introducing and finishing phosphorus accounts for introduces 10～90%, preferred 50～75% of total phosphorus in the molecular sieve; The phosphorus of introducing after transition metal is introduced and the atomic molar of introducing transition metal in the molecular sieve than the mol ratio of phosphorus atom and atoms metal (namely take) as 0.25～10: 1, be preferably 0.5～2.5: 1; Introduce before the transition metal or with the transition metal phosphorus of introducing simultaneously and the atomic molar ratio of introducing transition metal in the molecular sieve and be preferably 0.5～4.0: 1.The introducing of every a part of phosphorus can be carried out one or many.
The MFI structure molecular screen of described ammonium exchange, it is ammonium type or Hydrogen MFI structure molecular screen, sodium type molecular sieve that can be by will having the MFI structure is according to molecular sieve: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (5～10) obtains in room temperature to the 100 ℃ method that lower exchange was filtered after 0.3～1 hour.Filter cake after wherein filtering can roasting or not roasting.The MFI structure molecular screen sodium oxide content of described ammonium exchange preferably is not higher than 0.2 % by weight.Described MFI structure molecular screen can be ZSM-5, ZSM-8 and ZSM-11, wherein preferred ZSM-5.
The preparation method of the MFI structure molecular screen of phosphorous and transition metal provided by the present invention, preferred, the sodium type molecular sieve that will have a MFI structure is according to molecular sieve: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (5～10) is filtered after 0.3～1 hour in room temperature to 100 a ℃ lower exchange, with P contained compound solution and the solution that contains transistion metal compound molecular sieve is flooded modification again, wherein carry out twice at least with the P contained compound solution impregnation, and behind the transistion metal compound dipping, carry out at least one times; Preferred P contained compound solution impregnation is carried out at twice, before containing the transistion metal compound solution impregnation, carry out for the first time or with contain transistion metal compound solution and flood simultaneously (this moment, dipping solution contained phosphorus compound and transistion metal compound); For the second time be to carry out after the transistion metal compound solution impregnation is finished containing, dipping obtains product by dry, calcination process for the second time.Preferably, describedly with P contained compound solution and the solution that contains transistion metal compound the process that molecular sieve floods modification is carried out in the following way:
The mixed impregnant liquor of the part P contained compound of the filter cake after the ammonium exchange and calculated amount and metal-containing compound ℃ is mixed in room temperature to 95, be roasting under 400～800 ℃ the condition in temperature after dry or dry, ℃ mix in room temperature to 95 with remaining P contained compound steeping fluid again, drying is in 400～800 ℃ of roasting temperatures.Described drying is for example dried.
Among the MFI structure molecular screen preparation method of phosphorous and transition metal provided by the invention, described P contained compound can be selected from one or more of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate.
Among the preparation method of the MFI structure molecular screen of phosphorous and transition metal provided by the invention, described ammonium salt is water miscible ammonium salt, can be the inorganic ammonium salt of commonly using, and for example can be one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture.
Among the MFI structure molecular screen preparation method of phosphorous and transition metal provided by the invention, described transistion metal compound is selected from the water-soluble salt of described transition metal, and described water-soluble salt is selected from a kind of in vitriol, nitrate, the chlorate.
Among the MFI structure molecular screen preparation method of phosphorous and transition metal provided by the invention, described calcination process process also can be to carry out under water vapour atmosphere.
The preparation method of the MFI structure molecular screen of phosphorous and transition metal provided by the invention, the MFI structure molecular screen of described phosphorous and transition metal, 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
xO
y(70～97) SiO
2, be preferably: (0～0.2) Na
2O (0.9～5.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M.Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably.The MFI structure molecular screen rich surface phosphorus of resulting phosphorous and transition metal, its surperficial phosphorus content carries out Infrared Characterization with trimethylpyridine as probe molecule greater than its body phase phosphorus content, in its infrared spectrum at 1633cm
-1The place shows that without L acid charateristic avsorption band outside surface does not have L acid substantially, and the outside surface metal center is covered by phosphorus.
The MFI structure molecular screen of phosphorous and transition metal provided by the invention carries out Infrared Characterization with trimethylpyridine as probe, and its spectrogram is at 1633cm
-1The place is without absorption peak.Carry out Infrared Characterization with trimethylpyridine as probe and be existing method, its process is as follows: with the sample compressing tablet, place the original position pond of infrared spectrometer to seal, be evacuated down to 10 under 450 ℃
-3Pa, roasting 1.5h is cooled to room temperature; Then the trimethylpyridine steam that imports to the original position pond is kept adsorption equilibrium 30min, takes the photograph spectrum.The MFI structure molecular screen of described phosphorous and transition metal, its anhydrous chemical expression is preferably with the weighing scale of oxide compound: (0～0.2) Na
2O (0.9～5.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2Described MFI structure molecular screen can be ZSM-5, ZSM-8 and ZSM-11, wherein preferred ZSM-5.Among the present invention, described room temperature can be 15～30 ℃.
The molecular sieve rich surface phosphorus of phosphorous and transition metal provided by the invention, the phosphorus content on its molecular sieve surface is higher than the body phase phosphorus content of molecular sieve, represent the surperficial phosphorus content of molecular sieve and the ratio of the body phase phosphorus content of molecular sieve with Phosphorous distribution D, its Phosphorous distribution D satisfies D＞1, be preferably (1.05～9): 1, D=P wherein
(S)/ P
(C), described P
(S)Expression adopt zeolite crystal that the TEM-EDX method characterizes from the edge 1/10th phosphorus content to the center, P
(C)The phosphorus content of expression zeolite crystal center.
Below by embodiment the present invention is further described, but content not thereby limiting the invention.
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 5.6gH
3PO
4(concentration 85 % by weight) and 8.1gFe (NO
3)
39H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of roastings 2 hours, obtains sample; With 3.4gH
3PO
4(concentration 85 % by weight) are dissolved in the 90g water and obtain steeping fluid, with this steeping fluid and above-mentioned sample mix dipping, oven dry, 550 ℃ of roastings 2 hours, namely get molecular sieve of the present invention.Elementary analytical chemistry consists of 0.08Na
2O3.0Al
2O
35.4P
2O
51.5Fe
2O
389.3SiO
2The phosphorus of introducing for the second time accounts for 38%.
Comparative Examples 1
Prepare phosphorous and transition metal and have the molecular sieve of MFI structure by the method for CN1425567A.
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 9.0gH
3PO
4(concentration 85%) and 8.1gFe (NO
3)
39H
2O is dissolved in the 90g water, dries with the filter cake hybrid infusion; The gained sample namely gets the contrast molecular sieve 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.08Na
2O3.0Al
2O
35.4P
2O
51.5Fe
2O
389.3SiO
2
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 6.1gH
3PO
4(concentration 85%) and 30gCo (NO
3)
26H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, the gained sample with by 3.2gH
3PO
4(concentration 85%) is dissolved in the steeping fluid hybrid infusion that obtains in the 90g water, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.11Na
2O2.8Al
2O
35.5P
2O
58.6Co
2O
383SiO
2The phosphorus of introducing for the second time accounts for 34%.
Comparative Examples 2
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 9.3gH
3PO
4(concentration 85%) and 30gCo (NO
3)
26H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.11Na
2O2.8Al
2O
35.5P
2O
58.6Co
2O
383SiO
2
Embodiment 3
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 1.5gH
3PO
4(concentration 85%) and 3.8gNi (NO
3)
26H
2O dissolves in 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, obtains sample A3; Add 1.0gH
3PO
4(concentration 85%) dissolves in 90g water, with this steeping fluid and above-mentioned sample A3 hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.1Na
2O3.2Al
2O
31.5P
2O
51.0NiO94.2SiO
2The phosphorus of introducing for the second time accounts for 40%.
Comparative Examples 3
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 2.5gH
3PO
4(concentration 85%) and 3.8gNi (NO
3)
26H
2O dissolves in 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.1Na
2O3.2Al
2O
31.5P
2O
51.0NiO94.2SiO
2
Embodiment 4
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 7.7gH
3PO
4(concentration 85%) and 6gCuCl
2Be dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, obtain sample A4; With 4.3gH
3PO
4(concentration 85%) is dissolved in the 90g water, with this steeping fluid and above-mentioned sample A4 hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.11Na
2O2.9Al
2O
37.0P
2O
53.3CuO86.7SiO
2The phosphorus of introducing for the second time accounts for 36%.
Comparative Examples 4
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 12gH
3PO
4(concentration 85%) and 6gCuCl
2Be dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.11Na
2O2.9Al
2O
37.0P
2O
53.3CuO86.7SiO
2
Embodiment 5
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 3.9gH
3PO
4(concentration 85%) and 33.2gMn (NO
3)
2Be dissolved in the 90g water, this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of roastings were obtained sample A5 in 2 hours; With 1.6gH
3PO
4(concentration 85%) is dissolved in the 90g water, with this steeping fluid and above-mentioned sample A5 hybrid infusion, oven dry, 550 ℃ of roastings 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.12Na
2O3.0Al
2O
33.5P
2O
56.0Mn
2O
387.4SiO
2The phosphorus of introducing for the second time accounts for 29%.
Comparative Examples 5
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 5.5gH
3PO
4(concentration 85%) and 33.2gMn (NO
3)
2Be dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of roastings 2 hours.Elementary analytical chemistry consists of 0.12Na
2O3.0Al
2O
33.5P
2O
56.0Mn
2O
387.4SiO
2
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 2.4gH
3PO
4(concentration 85%) and 6.6gZn (NO
3)
26H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, obtains sample A6; With 1.1gH
3PO
4(concentration 85%) is dissolved in the 90g water, with this steeping fluid and above-mentioned sample A6 hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.12Na
2O3.1Al
2O
32.5P
2O
51.8ZnO92.5SiO
2The phosphorus of introducing for the second time accounts for 31%.
Comparative Examples 6
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 3.5gH
3PO
4(concentration 85%) and 6.6gZn (NO
3)
26H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.12Na
2O3.1Al
2O
32.5P
2O
51.8ZnO92.5SiO
2
Embodiment 7
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 3.0gH
3PO
4(concentration 85%) and 3.8gSnCl
45H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, obtains sample A7; With 2.1gH
3PO
4(concentration 85%) is dissolved in the 90g water, with this steeping fluid and above-mentioned sample A7 hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of:
0.1Na
2O·3.1Al
2O
3·3.5P
2O
5·1.7SnO
2·91.6SiO
2。The phosphorus of introducing for the second time accounts for 41%.
Comparative Examples 7
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 5.1gH
3PO
4(concentration 85%) and 3.8gSnCl
45H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.1Na
2O3.1Al
2O
33.5P
2O
51.7SnO
291.6SiO
2
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 2.8gH
3PO
4(concentration 85%) and 2.4gBi (NO
3)
35H
2O is dissolved in the 90g water, and this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process were obtained sample A8 in 2 hours; With 1.9gH
3PO
4(concentration 85%) is dissolved in the 90g water, with this steeping fluid and above-mentioned sample A8 hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.1Na
2O3.1Al
2O
33.2P
2O
51.1Bi
2O
392.5SiO
2The phosphorus of introducing for the second time accounts for 40%.
Comparative Examples 8
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 4.7gH
3PO
4(concentration 85%) and 2.4gBi (NO
3)
35H
2O is dissolved in the 90g water, with this steeping fluid and filter cake hybrid infusion, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.1Na
2O3.1Al
2O
33.2P
2O
51.1Bi
2O
392.5SiO
2
Embodiment 9
With 50gNH
4Cl is dissolved in the 1000g water, and (the catalyzer asphalt in Shenli Refinery 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=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 3.1gH
3PO
4(concentration 85%) and 8.2gFe (NO
3)
39H
2O, 2.2gBi (NO
3)
35H
2O dissolves in 90g water, and this steeping fluid and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process were obtained for the first time impregnated sample in 2 hours; Add 2.1gH
3PO
4(concentration 85%) dissolves in 90g water, with this steeping fluid and above-mentioned first time impregnated sample hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, namely gets molecular sieve of the present invention.Elementary analytical chemistry consists of 0.1Na
2O3.1Al
2O
33.1P
2O
51.6Fe
2O
31.0Bi
2O
391.1SiO
2Also can be expressed as 0.1Na
2O3.1Al
2O
33.1P
2O
52.6M
2O
391.1SiO
2, wherein the calculating nucleidic mass of M is 82.9.The phosphorus of introducing for the second time accounts for 40%.
Comparative Examples 9
With 50gNH
4Cl is dissolved in the 1000g water, and (catalyzer branch office in Shandong produces, and has the amine method synthetic, SiO to add 100g (butt) crystallization product ZSM-5 molecular sieve in this solution
2/ Al
2O
3=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 5.2gH
3PO
4(concentration 85%) and 8.2gFe (NO
3)
39H
2O, 2.2gBi (NO
3)
35H
2O dissolves in 90g water, with this steeping fluid and the even hybrid infusion of filter cake, oven dry; The gained sample namely gets molecular sieve of the present invention 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.1Na
2O3.1Al
2O
33.1P
2O
51.6Fe
2O
31.0Bi
2O
391.1SiO
2Also can be expressed as 0.1Na
2O3.1Al
2O
33.1P
2O
52.6M
2O
391.1SiO
2, wherein the calculating nucleidic mass of M is 82.9.
Embodiment 10
Phosphorous distribution in the modified molecular screen of present embodiment explanation the inventive method preparation.
The sample that embodiment 1 and Comparative Examples 1 are made with TEM-EDS to Fe
2O
3And P
2O
5Distribution characterize, the results are shown in Fig. 1.
As can be seen from Figure 1, in the sample that Comparative Examples 1 makes, Fe
2O
3And P
2O
5Equally distributed in body phase and surface, in the sample that embodiment 1 makes, Fe
2O
3Equally distributed in body phase and surface, and P
2O
5Then at surface enrichment.
The surperficial phosphorus of the ZSM-5 molecular sieve of the phosphorous and transition metal that embodiment 1～9 is prepared and the body mutually measuring result of the ratio of phosphorus content see Table 1.
Table 1
Embodiment 11
The modified molecular screen outer surface acidity of present embodiment explanation the inventive method preparation.
The sample that embodiment 1 and Comparative Examples 1 are made is made probe with trimethylpyridine it is carried out Infrared Characterization, the results are shown in Fig. 2.
As can be seen from Figure 2, Comparative Examples 1 is at 1633cm
-1There is the infrared signature absorption peak of L acid at the place, and embodiment 1 does not have absorption peak herein.Its trimethylpyridine absorption infrared spectrum of embodiment 2～9 resulting molecular sieves is herein also without absorption peak.The trimethylpyridine molecular dimension is larger, can't enter in the molecular sieve pore passage, sign be the acidity of molecular sieve outer surface, show that the L acid site on the MFI structure molecular screen outside surface metal of phosphorous and transition metal provided by the invention is covered by phosphorus.
Embodiment 12
The present embodiment explanation adopts the molecular sieve of the inventive method preparation to be used for catalytic cracking of petroleum hydrocarbon, for the productive rate of propylene and optionally impact.
The sample that above-described embodiment and Comparative Examples are made carries out 800 ℃, 100% steam at the fixed bed aging equipment respectively to be processed in aging 4 hours, then use the industrial poiser of catalyzer DOCP (production of Chang Ling catalyst plant) to make base catalyst, convert evenly by 90: 10 weight ratio is mixed with each molecular sieve respectively, and compressing tablet sieves out 20-40 purpose particle, instead estimate 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 (weight ratio) 2.94, catalyst inventory 5g.
Stock oil character sees Table 2.Evaluation result is listed in table 3.
As can be seen from Table 3, after in catalytic cracking catalyst, adding modification MFI structure molecular screen provided by the invention, compare with the result of Comparative Examples, change in the little situation at transformation efficiency, liquefied gas yield improves slightly to some extent, propylene, iso-butylene yield and selectivity significantly improve, and coke, dry gas yied reduce, and hydrogen yield obviously reduces.
Table 2
Claims (13)
1. the preparation method of the MFI structure molecular screen of a phosphorous and transition metal, be included in the molecular sieve with MFI structure of ammonium exchange and introduce phosphorus and transition metal, wherein, described phosphorus divides two portions to introduce, part phosphorus is introduced after transition metal is introduced, and a part of phosphorus is introduced before introducing transition metal or with transition metal simultaneously in addition; The MFI structure molecular screen of described phosphorous and transition metal, 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
xO
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more among Fe, Co, Ni, Cu, Mn, Zn, Sn, the Bi.
2. in accordance with the method for claim 1, it is characterized in that the phosphorus of introducing after transition metal is introduced accounts for 10～90% of total phosphorus in the molecular sieve.
3. in accordance with the method for claim 2, it is characterized in that the phosphorus of introducing after transition metal is introduced accounts for 25～50% of total phosphorus in the molecular sieve.
4. according to claim 2 or 3 described methods, it is characterized in that the atomic molar ratio of transition metal is 0.25～10: 1 in the phosphorus of introducing after transition metal is introduced and the molecular sieve.
5. according to each described method of claim 1～4, it is characterized in that, described phosphorus and the transition metal introduced in the molecular sieve with MFI structure of ammonium exchange comprises with P contained compound solution and the solution that contains transistion metal compound and described molecular sieve flooded modification, then drying, 400～800 ℃ of roastings; Wherein the P contained compound solution impregnation is carried out twice at least.
6. in accordance with the method for claim 5, it is characterized in that, describedly with P contained compound solution and the solution that contains transistion metal compound described molecular sieve is flooded modification and comprise: the filter cake after the ammonium exchange is mixed with the solution of metal-containing compound with the part P contained compound that comprises calculated amount, at 400～800 ℃ of roasting temperatures, the solution with the P contained compound that is left mixes again after dry or dry.
7. in accordance with the method for claim 5, it is characterized in that described P contained compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate or its mixture; Described transistion metal compound is selected from the water-soluble salt of described transition metal.
8. in accordance with the method for claim 1, it is characterized in that the molecular sieve preparation method with MFI structure of described ammonium exchange comprises: the sodium type molecular sieve that will have a MFI structure is according to molecular sieve: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (5～10) is filtered after 0.3～1 hour in room temperature to 100 a ℃ lower exchange.
9. the MFI structure molecular screen of a phosphorous and transition metal, 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
xO
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more among Fe, Co, Ni, Cu, Mn, Zn, Sn, the Bi; The infrared spectrum that the MFI structure molecular screen of described phosphorous and transition metal obtains as probe molecule with trimethylpyridine is at 1633cm
-1The place is without absorption peak.
10. according to molecular sieve claimed in claim 9, it is characterized in that, the MFI structure molecular screen of described phosphorous and transition metal, its anhydrous chemical expression is counted with the weight of oxide compound: (0～0.2) Na
2O (0.9～5.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2
11., it is characterized in that described MFI structure molecular screen is ZSM-5 according to molecular sieve claimed in claim 9.
12., it is characterized in that the surperficial phosphorus content of molecular sieve is greater than 1～9 with the ratio of the body phase phosphorus content of molecular sieve: 1 according to each described molecular sieve of claim 9～11.
13. the MFI structure molecular screen of a phosphorous and transition metal, 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
xO
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more among Fe, Co, Ni, Cu, Mn, Zn, Sn, the Bi; The MFI structure molecular screen rich surface phosphorus of described phosphorous and transition metal, the ratio of its surperficial phosphorus content and body phase phosphorus content is greater than 1.
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| CN106140271B (en) * | 2015-04-23 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
| CN106140270B (en) * | 2015-04-23 | 2019-02-01 | 中国石油化工股份有限公司 | Phosphorous and a kind of MFI structure molecular sieve and preparation method thereof containing carried metal |
| CN107974274B (en) * | 2016-10-21 | 2020-01-10 | 中国石油化工股份有限公司 | Phosphorus-containing and metal-loaded MFI structure molecular sieve and preparation method thereof |
| CN107899606A (en) * | 2017-11-30 | 2018-04-13 | 鹤壁博文科峰催化技术有限公司 | A kind of ferrophosphorus modified molecular screen and preparation method thereof |
| CN113526522B (en) * | 2020-04-13 | 2023-02-21 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| CN114505092B (en) * | 2020-10-28 | 2023-03-10 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent, preparation method and hydrocarbon oil catalytic cracking method |
| EP4137457A1 (en) * | 2020-04-13 | 2023-02-22 | China Petroleum & Chemical Corporation | Phosphorus-modified mfi-structured molecular sieve, catalytic cracking auxiliary agent and catalytic cracking catalyst containing phosphorus-modified mfi-structured molecular sieve, and preparation method therefor |
| CN114713277B (en) * | 2021-01-05 | 2023-07-14 | 中国石油化工股份有限公司 | Modified silicon-aluminum molecular sieve with MFI structure and preparation method thereof |
| CN112960680B (en) * | 2021-04-09 | 2022-09-30 | 陕西延长石油（集团）有限责任公司 | Modification method for improving hydrothermal stability of ZSM-5 molecular sieve |
| CN113526523A (en) * | 2021-08-26 | 2021-10-22 | 鄂尔多斯应用技术学院 | Mesoporous ZSM-5 molecular sieve with deep short pores and application thereof in preparation of pyridine base |
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| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN101234764A (en) * | 2007-01-31 | 2008-08-06 | 中国石油化工股份有限公司 | Method of preparing MFI structure molecular sieve containing phosphorus and transition metal |
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| CN1194181A (en) * | 1997-03-24 | 1998-09-30 | 中国石油化工总公司 | Phosphorus containing molecular sieve with MFI structure |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN101234764A (en) * | 2007-01-31 | 2008-08-06 | 中国石油化工股份有限公司 | Method of preparing MFI structure molecular sieve containing phosphorus and transition metal |
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