CN103084205B - Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof - Google Patents

Abstract

A cracking catalyst resistant to alkali nitrogen and producing liquefied gas and a preparation method thereof, the catalyst includes a cracking active component, a mesoporous silica-alumina material, a binder and clay, wherein the cracking active component includes a Y-type A molecular sieve and a molecular sieve with an MFI structure, the Y-type molecular sieve includes a rare earth content of 8-23% by weight as rare earth oxide, an iron content of _0.1-3.0 % by weight as _Fe2O3 , and a copper content of 0-3.0% by CuO. % by weight, the first Y-type molecular sieve with a phosphorus content of 0-2.0% by weight calculated as P ₂ O ₅ , and a sodium oxide content of 0.1-2.5% by weight. The preparation method of the catalyst comprises the steps of beating cracking active components, mesoporous silicon-aluminum materials, clay and binder, spray drying, washing, filtering and drying. The catalyst is used for catalytic cracking of base oil containing alkali nitrogen, and has high conversion rate and high yield of liquefied gas.

Description

A cracking catalyst resistant to alkali nitrogen and producing liquefied petroleum gas and its preparation method

technical field

The present invention relates to a catalytic cracking catalyst, more specifically to a cracking catalyst resistant to alkali nitrogen and prolific in producing liquefied gas.

Background technique

Catalytic cracking (FCC) is an important secondary processing process of crude oil and occupies a pivotal position in the oil refining industry. In the catalytic cracking process, heavy fractions such as vacuum distillate oil or residues of heavier components react in the presence of catalysts and are converted into high value-added products such as liquefied gas, gasoline, and diesel oil. In this process, it is usually necessary to use Catalytic material with high cracking activity. Microporous zeolite catalytic materials are widely used in petroleum refining and processing industries due to their excellent shape-selective catalytic performance and high cracking reactivity. With the depletion of petroleum resources and the requirements of environmental protection, especially the growing trend of crude oil becoming heavier and the market's large demand for light oil products, more and more attention is paid to the depth of heavy oil and residual oil in the petroleum processing industry processing.

Recently, with the increasingly heavy and inferior quality of catalytic cracking feedstock oil, blending low-quality raw materials such as coker gas oil (CGO) has become an important way for refineries to expand the source of catalytic cracking feedstock and tap the potential to increase efficiency. Compared with straight-run gas oil, coker gas oil is an inferior catalytic feedstock with higher nitrogen content, aromatic hydrocarbon content and colloid content, and lower saturated hydrocarbon content. Increasing the blending ratio of coker gas oil will seriously affect catalytic cracking Normal operation of the plant, resulting in lower conversion and a marked deterioration in product distribution. Studies have shown that the nitrogen compounds in coker wax oil, especially the basic nitrogen compounds (the nitrogen atoms in which are called basic nitrogen) are the direct cause of this consequence. Basic nitrogen compounds have a strong adsorption capacity due to their lone pair of electrons. And complexing performance, so it is easy to interact with the acidic center on the catalyst, resulting in a decrease in the activity of the catalyst. Moreover, nitrogen-containing compounds are more likely to be adsorbed on the acidic center of the catalyst than polycyclic aromatic hydrocarbons, which are easy to form agglomeration points and promote coke formation, that is, nitrogen-containing compounds can be regarded as coke precursors that are easier to adsorb.

To overcome the problem of catalyst activity decline caused by basic nitrogen compounds, currently adopted methods such as the process means mentioned in CN1088246A, US7744745 and US5660716, and the method for complexing and removing basic nitrogen compounds mentioned in US4846962.

The most economical and effective method to overcome the decline in catalyst activity caused by basic nitrogen compounds is to use cracking catalysts or additives resistant to basic nitrogen compounds in the catalytic cracking process. However, the existing cracking catalysts still have the problems of low activity and poor product distribution when used in raw materials containing alkali nitrogen, and no cracking catalysts related to alkali nitrogen resistance and high production of liquefied gas have been found.

Contents of the invention

The technical problem to be solved by the present invention is to provide a kind of catalytic cracking catalyst resistant to alkali nitrogen and prolific liquefied gas. /g of raw oil) catalytic cracking, with a higher conversion rate and liquefied gas yield.

The invention provides a catalytic cracking catalyst resistant to alkali and nitrogen and capable of producing liquefied gas. The catalytic cracking catalyst contains 10-70% by weight of cracking active components, 1-20% by weight of mesoporous silicon-aluminum materials, and 10-70% by weight of clay and 10-60% by weight of binder, wherein the cracking active components include 70-85% by weight of Y-type molecular sieves and 15-30% by weight of MFI molecular sieves, and the Y-type molecular sieves include the first Y Type molecular sieve, wherein, the first Y-type molecular sieve is a Y-type molecular sieve modified with rare earth, iron, copper, phosphorus, the rare earth content in the molecular sieve is 8-23% by weight as rare earth oxide, and the iron content is _{Fe2O 3} is 0.1-3.0 wt%, the copper content is 0-3.0 wt% as CuO, the phosphorus content _is 0-2.0 wt% as _P2O5 , and the sodium oxide content is 0.1-2.5 wt%.

Based on the total weight of the cracking active component, the cracking active component contains 70-85% by weight of Y-type molecular sieve and 15-30% by weight of MFI structure molecular sieve; based on the total weight of the Y-type molecular sieve , the Y-type molecular sieve includes 20-100% by weight of the first Y-type molecular sieve and 0-80% by weight of other Y-type molecular sieves, and the other Y-type molecular sieves are the second Y-type molecular sieve and/or the third Y-type molecular sieve , wherein the second Y-type molecular sieve is rare earth-containing DASY molecular sieve, and its rare earth content is preferably 1.5-3% by weight; the rare earth content in the third Y-type molecular sieve is 12-16% by weight in terms of rare earth oxides, The phosphorus content calculated as P ₂ O ₅ is 0.5-7% by weight. In the ³¹ P MAS NMR spectrum of the molecular sieve, the peak area of the resonance signal with a chemical shift of -14 ± 2ppm and -23 ± 2ppm accounts for a percentage of the total peak area greater than 85%, in the ²⁷ Al MAS NMR spectrum of the molecular sieve, the peak area of the resonance signal with a chemical shift of 0±2ppm accounts for more than 20% of the total peak area.

The cracking active component contains a first Y-type molecular sieve, and the first Y-type molecular sieve is a Y-type molecular sieve containing rare earth, iron or iron and copper, containing or not containing phosphorus, and the rare earth content is 8-23% in terms of rare earth oxide. % by weight, the iron content is 0.1-3.0 wt% as _Fe2O3 , the copper content is 0-3.0 _wt % as CuO, the phosphorus content _is 0-2.0 wt% as _P2O5 , and the sodium oxide content is 0.1 -2.5% by weight.

The first Y-type molecular sieve can be prepared by modifying the Y-type molecular sieve through the following process. The process includes: using NaY molecular sieve as raw material, undergoing rare earth exchange and roasting to obtain "one cross one roast" RENaY; Iron-containing substances, copper-containing substances, phosphorus-containing substances, and ammonium salts may or may not be reacted to obtain a Y molecular sieve product modified with rare earth and iron/copper/phosphorus, which is the active component of the modified Y molecular sieve.

Wherein, the described process of obtaining "one-baking" RENaY is well known to those skilled in the art, usually, NaY and rare earth compound are mixed in NaY:RE ₂ O ₃ =1:0.10-0.25 (weight ratio), pH= 2.0-4.5, exchange temperature at 25-100°C for 0.3-1.5 hours, filter, wash, and filter cake at 400-850°C, 0-100% steam for more than 0.3 hours to obtain. The further described process of obtaining Y molecular sieve products modified with rare earth and iron/copper/phosphorus is to combine RENaY with rare earth compounds, iron-containing, copper-containing, phosphorus-containing substances, with or without ammonium salts, according to the composition of the target product Under the circumstances, according to NaY _{: RE2O3} : _Fe2O3 / _CuO : _P2O5 :ammonium salt=1 _: 0.02-0.15:0.001-0.05:0-0.04:0-0.5 (weight ratio), pH= 2.0-4.5, react at 20-100°C, then filter and wash.

The MFI structure molecular sieve can be a first MFI structure molecular sieve and/or a second MFI structure molecular sieve, wherein,

The anhydrous chemical composition expression in terms of molar ratio of oxides in the first MFI structure molecular sieve is: (0.01-025)RE ₂ O ₃ ·(0.005-0.02)Na ₂ O·Al ₂ O ₃ ·(0.2 -1.0)P ₂ O ₅ ·(35-120)SiO ₂ , the adsorption weight ratio of the molecular sieve to n-hexane and cyclohexane is 4-5;

The anhydrous chemical composition expression of the second MFI structure molecular sieve in terms of oxide weight ratio is: (0-03)Na ₂ O·(0.5-5.5)Al ₂ O ₃ ·(1.3-10)P ₂ O ₅ ·(0.7-15)M1 _x O _y ·(0.01-5)M2 _m O _n ·(70-97)SiO ₂ , where M1 is Fe, Co or Ni, x represents the atomic number of M1, and y represents the satisfaction of M1 The number of oxygen required for the oxidation state, M2 is selected from Zn, Mn, Ga or Sn, m represents the number of atoms of M2, and n represents the number of oxygen required to meet the oxidation state of M2.

The present invention also provides a preparation method of the described catalytic cracking catalyst that resists alkali nitrogen and produces liquefied gas more, the method comprising:

The cracking active component, the mesoporous silica-alumina material, the clay and the binder are mixed and beaten, and then spray-dried, washed, filtered and dried in sequence.

The catalytic cracking catalyst for resisting nitrogen reduction and producing liquefied gas provided by the present invention is particularly suitable for catalytic cracking of heavy oil, especially when the content of basic nitrogen compounds in the raw oil is relatively high, for example, the content of basic nitrogen is about 900-2000 μg /g, the catalytic cracking catalyst for anti-nitrogen reduction and high production of liquefied gas provided by the present invention can show higher catalytic cracking activity in the process of catalytic cracking of heavy oil, can obtain higher conversion rate, and obtain higher yield of liquefied gas Rate.

Detailed ways

The catalytic cracking catalyst for alkali nitrogen resistance and high yield of liquefied gas provided by the present invention contains cracking active components, mesoporous silicon-aluminum materials, clay and binder, wherein the cracking active components contain a modified Y-type Molecular sieve (i.e. the first Y-type molecular sieve of _the present invention), the molecular sieve is modified with rare earth, iron, copper, phosphorus, the rare earth content in the molecular sieve is 8-23% by weight as rare earth oxide, and the iron content is _Fe2O3 The calculation is 0.1-3.0 wt%, the copper content is 0-3.0 wt% as CuO, the phosphorus content is 0-2.0 wt% as P ₂ O ₅ , and the sodium oxide content is 0.1-2.5 wt%.

Preferably, the rare earth content in the first Y-type molecular sieve is 10-20% by weight as rare earth oxide, the iron content _is 0.5-2.5% by weight as _Fe2O3 , and the copper content is 0.2-1.5% by weight as CuO , the phosphorus content is 0-1.0% by weight based on P ₂ O ₅ .

More preferably, the rare earth content in the first Y-type molecular _sieve is 14-20 wt% as rare earth oxide, the iron content is 0.6-1.0 wt% as _Fe2O3 , and the copper content is 0.5-1.2 wt% as CuO %, the phosphorus content is 0-1.0% by weight based on P ₂ O ₅ , and the sodium oxide content is 0.1-2.0% by weight.

The first Y-type molecular sieve is prepared by modifying the Y-type molecular sieve through the following process. The process includes: using NaY molecular sieve as raw material, through rare earth exchange and roasting, to obtain "one cross one roast" RENaY; , iron-containing substances, copper-containing substances, phosphorus-containing substances, and or not react with ammonium salts to obtain a Y molecular sieve product modified with rare earth and iron/copper/phosphorus, which is the first Y-type molecular sieve.

Wherein, the process of "cross-baking" RENaY is well known to those skilled in the art, usually NaY and rare earth compound are mixed in NaY:RE ₂ O ₃ =1:0.10-0.25 (weight ratio), pH=2.0 -4.5, exchange temperature at 25-100°C for 0.3-1.5 hours, filter, wash, and filter cake at 400-850°C, 0-100% steam for more than 0.3 hours to obtain. Further, the process of obtaining the first Y-type molecular sieve (that is, Y molecular sieve modified with rare earth, iron, copper, phosphorus) product is to combine RENaY with rare earth compounds, iron-containing, copper-containing, and phosphorus-containing Phosphorous substances, with or without ammonium salts, as NaY:RE ₂ O ₃ :Fe ₂ O ₃ /CuO:P ₂ O ₅ :ammonium salts=1:0.02-0.15:0.001-0.05:0-0.04: 0-0.5 (weight ratio), pH=2.0-4.5, react at 20-100°C, then filter and wash.

In the above modification process, the rare earth compound is rare earth chloride, rare earth nitrate or rare earth sulfate, preferably rare earth chloride. It can be a single rare earth element or a mixture of different rare earth elements.

The iron-containing substance may be selected from salts of iron in different valence states, such as one or more of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, and ferrous sulfate.

The copper-containing substance may be selected from salts of copper in different valence states, such as one or more of copper chloride, cuprous chloride, copper nitrate, cuprous nitrate, and copper sulfate.

The phosphorus-containing substance is selected from phosphoric acid or its salts, such as one or more mixtures of ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.

Described ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium bisulfate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, wherein preferred Ammonium Chloride and/or Ammonium Sulfate.

Compared with conventional rare earth Y molecular sieves, the first Y-type molecular sieve has a higher acid content, especially a higher external surface acid content, when the rare earth content is equivalent. The acid content of the modified Y-type molecular sieve was determined by ³¹ P MAS NMR after adsorbing tributyl phosphorus oxide (TBPO, dynamic diameter 0.82nm) through the acid content characterization method of adsorbing tributyl phosphorus oxide and adsorbing trimethyl phosphorus oxide 1.400-4.500mmol·g ^-1 , since the molecular dynamic diameter of TBPO is 0.82nm, which is larger than the pore size of the molecular sieve, it cannot enter the pore channel of the molecular sieve, so it represents the acidity on the outer surface of the molecular sieve; and the modified Y-type molecular sieve After the adsorption of trimethylphosphorus oxide (TMPO), the molecular sieve acid content determined by ³¹ P MAS NMR is 2.300-6.600 mmol·g ^-1 . Since the dynamic diameter of TMPO molecules is 0.55 nm, they can enter the pores of molecular sieves, so its characterization is the bulk acid content of the molecular sieve.

The first Y-type molecular sieve of the present invention, by using NaY as a raw material, introduces a higher rare earth content through two rare earth exchanges, which improves the activity and stability of the molecular sieve; the introduction of iron/copper/phosphorus plays a role in regulating the acid center The effect of strength and density, at the same time, because the electron distribution of iron and/or copper ions has d empty orbitals, it is beneficial to form complexes with nitrogen atoms containing lone pair electrons to selectively adsorb basic nitrides, reducing the impact of basic nitrogen on The poisoning effect of the acid center of the molecular sieve, and the first Y-type molecular sieve has more acid content on the outer surface, which is conducive to effectively resisting the poisoning effect of the alkali nitrogen macromolecule on the acid center of the molecular sieve as an active component, so that the obtained The modified Y-type molecular sieve exhibits excellent alkali nitrogen resistance. Therefore, it is beneficial that the catalyst provided by the invention has remarkable alkali nitrogen resistance.

In order to improve the catalytic cracking activity of the catalytic cracking catalyst of the present invention, which is resistant to alkali nitrogen and produces liquefied gas, in the process of catalytic cracking of heavy oil with a higher content of basic nitrogen compounds, so as to obtain an improved conversion rate and improve the Quality oil is converted into the activity of liquefied gas, to improve the yield of liquefied gas, preferably, based on the total weight of the cracking active components, the cracking active components contain 70-85% by weight of Y-type molecular sieve components and 15-30% by weight of molecular sieve components of MFI structure. In the present invention, the weight proportions of the Y-type molecular sieve component and the MFI structure molecular sieve component in the cracking active component are calculated on a dry basis.

The active components of the present invention include Y-type molecular sieves, and the Y-type molecular sieves may also include other molecular sieves except the first Y-type molecular sieves. Based on the total weight of the Y-type molecular sieves, the The Y-type molecular sieve includes 20-100% by weight of the first Y-type molecular sieve and 0-80% by weight of other Y-type molecular sieves. The other Y-type molecular sieves can be the second Y-type molecular sieve and/or the third Y-type molecular sieve, the second Y-type molecular sieve is a rare earth-containing DASY molecular sieve, and the rare earth-containing DASY molecular sieve is a rare earth-containing hydrothermal The ultrastable molecular sieve wherein the rare earth content calculated as RE ₂ O ₃ (rare earth oxide) is preferably 1.5-3.0% by weight. The rare earth-containing DASY molecular sieve can be various commercially available products, for example, it can be DASY2.0 molecular sieve purchased from Sinopec Catalyst Qilu Branch.

The rare earth content in the third Y-type molecular sieve is 12-16% by weight in terms of rare earth oxides, and the phosphorus content in terms of P ₂ O ₅ is 0.5-7% by weight. In the 31P MAS NMR spectrum of the molecular sieve, the chemical shift The peak area of the -14±2ppm and -23±2ppm resonance signals accounts for more than 85% of the total peak area. In the 27Al MAS NMR spectrum of the molecular sieve, the peak area of the resonance signal with a chemical shift of 0±2ppm accounts for the percentage of the total peak area Greater than 20%.

Preferably, the phosphorus content calculated as P ₂ O ₅ in the third Y-type molecular sieve is 1-3% by weight.

Preferably, in the ³¹ P MAS NMR spectrum of the third Y-type molecular sieve, the peak areas of resonance signals with chemical shifts of -14±2ppm and -23±2ppm account for more than 90% of the total peak area. Preferably, the unit cell constant of the third Y-type molecular sieve is

In the present invention, the third Y-type molecular sieve can be prepared according to the existing method, and the specific preparation method can refer to the patent application CN101088917A, especially the examples 1-4 therein.

In the present invention, the adsorption weight ratio of the first MFI structure molecular sieve to normal hexane and cyclohexane is 4-5, in terms of the molar ratio of oxides, its anhydrous chemical composition expression is: (0.01-0.25 )RE ₂ O ₃ ·(0.005-0.02)Na ₂ O·Al ₂ O ₃ ·(0.2-1.0)P ₂ O ₅ ·(35-120)SiO ₂ .

The X-ray diffraction spectrum data of the first molecular sieve with MFI structure are shown in Table 1 below, and the relative intensity values represented by the symbols in the table are shown below. In Table 1 below, VS: 80-100%; S: 60- 80%; M: 40-60%; W: 20-40%; VW: <20%.

Table 1

d value (×10 ^-1 nm) I/I ₀ 11.2±0.2 VS 10.1±0.2 m 9.8±0.2 VW 3.85±0.04 VS 3.81±0.04 S 3.75±0.04 W 3.72±0.04 m 3.65±0.04 m 3.60±0.04 W

In the first molecular sieve with MFI structure, the rare earth is contained in the molecular sieve crystal. The rare earths come from the rare earth-containing faujasite seeds used in the synthesis of molecular sieves.

In the first MFI structure molecular sieve, phosphorus is chemically bound to aluminum in the framework of the molecular sieve, which has a coordination corresponding to Al(4Si) in the ²⁷ Al NMR spectrum (i.e., Al originates from the formation of four Si atoms through oxygen. Tetrahedral structure), the chemical shift is 55ppm spectrum peak, and there is a spectrum peak corresponding to Al(4P) coordination (that is, the Al atom forms a tetrahedral structure through oxygen and four P atoms), the chemical shift is 39ppm; In the ³¹ P NMR spectrum, the molecular sieve has a peak corresponding to the P(4Al) coordination (that is, the interaction between the PO ₄ tetrahedron and the adjacent AlO ₄ tetrahedron) and a chemical shift of -29ppm.

Preferably, the phosphorus in the molecular sieve with the first MFI structure is evenly distributed in the crystal phase of the molecular sieve. The analysis results of transmission electron microscope-energy dispersive spectroscopy (TEM-EDS) show that the phosphorus content in any single crystal particle is similar to that in the molecular sieve bulk phase.

The adsorption weight ratio of the first MFI structure molecular sieve to n-hexane and cyclohexane is 4-5, under the conditions that the adsorption temperature is 40°C, the adsorption time is 3 hours, and the adsorption phase pressure P/P ₀ =0.20-0.25 , the adsorption capacity of the molecular sieve to n-hexane is 98-105 mg/g, and the adsorption capacity to cyclohexane is 20-25 mg/g. where _P0 is the saturated vapor pressure.

In the present invention, the first molecular sieve with MFI structure can be prepared according to the existing method, and the specific preparation method can refer to the patent application CN1147420A, especially the examples 1-6 therein.

In the present invention, the anhydrous chemical composition expression of the second MFI structure molecular sieve in terms of oxide weight ratio is: (0-0.3)Na ₂ O·(0.5-5.5)Al ₂ O ₃ ·(1.3- 10)P ₂ O ₅ ·(0.7-15)M1 _x O _y ·(0.01-5)M2 _m O _n ·(70-97)SiO ₂ , where M1 is Fe, Co or Ni, and x represents the atom of M1 Number, y represents the number of oxygen required to meet the M1 oxidation state, M2 is selected from Zn, Mn, Ga or Sn, m represents the number of atoms of M2, and n represents the number of oxygen required to meet the M2 oxidation state.

Preferably, the molecular sieve with the second MFI structure is (0-0.2)Na ₂ O·(0.9-5.0)Al ₂ O ₃ ·(1.5-7)P ₂ O ₅ ·(0.9 -10) M1 _x O _y · (0.5-2) M2 _{m On} · (82-92) SiO ₂ .

In a preferred case, M1 is Fe and M2 is Zn.

In the present invention, the second molecular sieve with MFI structure can be prepared according to the existing method, and the specific preparation method can also refer to the patent application CN1611299A, especially the examples 1-11 therein.

In the present invention, the clay can be various clays conventionally used in catalytic cracking catalysts, for example, it can be selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retort clay One or more of , sepiolite, attapulgite, hydrotalcite and bentonite.

In the present invention, the binder can be various binders conventionally used in catalytic cracking catalysts, for example, it can be one or more selected from silica sol, aluminum sol and pseudo-boehmite, preferably Double aluminum binder for aluminum sol and pseudoboehmite.

The alkali nitrogen resistant catalytic cracking catalyst provided by the present invention also contains mesoporous silica-alumina material, preferably, the mesoporous silica-alumina material has a phase structure of pseudo-boehmite, anhydrous The chemical expression is: (0-0.3)Na ₂ O·(40-90)Al ₂ O ₃ ·(10-60)SiO ₂ , the average pore diameter is 8-20nm, the most probable pore diameter is 5-15nm, the ratio The surface area is 200-400m ² /g, the pore volume is 0.5-2.0ml/g; more preferably, the average pore diameter is 10-20nm, the most probable pore diameter is 10-15nm, the specific surface area is 200-400m ² /g, the pore The volume is 1.0-2.0ml/g. The mesoporous silica-alumina material can be prepared by the following method, which includes: neutralizing the aluminum source and alkali solution at room temperature to 85°C to form a gel, and the pH of the end point of gelation is 7-11; and then according to SiO ₂ : Al ₂ O ₃ =1:(0.6-9) weight ratio, adding silicon source, aging at room temperature to 90°C for 1-10 hours, and then filtering, the filter cake obtained by filtering is exchanged with ammonium, so that the content of sodium oxide does not exceed 0.3% by weight , then dried at 100-150°C and calcined at 350-650°C for 1-20 hours to obtain a mesoporous silica-alumina material, which can be directly used to prepare a catalyst, or, at room temperature to 80°C, with an acid-aluminum ratio of 0.1-0.3 The mesoporous silica-alumina material obtained by the above-mentioned roasting is contacted with the inorganic acid for 0.5-3 hours under certain conditions to obtain an acid-treated mesoporous silica-alumina material for preparing a cracking catalyst. The aluminum source may be various aluminum sources conventionally used in the art, for example, the aluminum source may be one or more selected from aluminum nitrate, aluminum sulfate or aluminum chloride. The silicon source can be various silicon sources conventionally used in the art, and the silicon source can be, for example, at least one of silica gel, water glass, sodium silicate, tetraethyl silicon, silicon oxide, silica sol and silica gel kind. The alkaline solution can be various alkaline solutions commonly used in this field, for example, it can be one or more of ammonia water, potassium hydroxide solution, sodium metaaluminate solution and sodium hydroxide solution. The mesoporous silica-alumina material and its preparation method can be referred to CN1565733A or CN1854258A, for example, Examples 1-9 of CN1854258A.

According to the catalytic cracking catalyst for alkali nitrogen resistance and high yield of liquefied gas provided by the present invention, based on the dry basis weight of the catalytic cracking catalyst, the content of the cracking active component is 10-70% by weight on a dry basis, so The content of the mesoporous silica-alumina material is 1-20% by weight on a dry basis, the content of the binder on a dry basis is 10-60% by weight, and the content of the clay on a dry basis is 10-70% by weight. % by weight, preferably, based on the dry basis weight of the catalytic cracking catalyst, the content of the cracking active component is 10-45% by weight on a dry basis, and the content of the mesoporous silica-alumina material is based on a dry basis The content of the clay is 2-15% by weight, the content of the clay is 20-40% by weight on a dry basis, and the content of the binder is 20-50% by weight on a dry basis.

The present invention also provides a kind of preparation method of the described catalytic cracking catalyst of resisting alkaline nitrogen and producing liquefied gas more, the method comprises the following steps:

(1) Using NaY molecular sieve as raw material, after rare earth exchange and roasting, "cross-baking" RENaY is obtained; then react with rare earth compounds, iron-containing substances, copper-containing substances, phosphorus-containing substances, and ammonium salts to obtain The Y molecular sieve product modified with rare earth and iron/copper/phosphorus is the active component of the first Y molecular sieve described in the present invention;

Wherein, the process of "cross-baking" RENaY is well known to those skilled in the art, usually NaY and rare earth compound are mixed in NaY:RE ₂ O ₃ =1:0.10-0.25 (weight ratio), pH=2.0 -4.5, exchange temperature at 25-100°C for 0.3-1.5 hours, filter, wash, and filter cake at 400-850°C, 0-100% steam for more than 0.3 hours to obtain. The further described process of obtaining Y molecular sieve products modified with rare earth and iron/copper/phosphorus is to combine RENaY with rare earth compounds, iron-containing, copper-containing, phosphorus-containing substances, with or without ammonium salts, according to the composition of the target product Under the circumstances, according to NaY _{: RE2O3} : _Fe2O3 / _CuO : _P2O5 :ammonium salt=1 _:0.02-0.15 :0.001-0.05:0-0.04:0-0.5 (weight ratio), pH= 2.0-4.5, react at 20-100°C, then filter and wash.

(2) Mix and beat the cracking active component, mesoporous silica-alumina material, clay and binder, and then perform spray drying, washing, filtering and drying in sequence, wherein the cracking active component contains Y-type molecular sieve components and Molecular sieve components with MFI structure;

The Y-type molecular sieve component includes the first Y-type molecular sieve, or includes the first Y-type molecular sieve and other Y-type molecular sieves, and the other Y-type molecular sieves are preferably second Y-type molecular sieves and/or The third Y-type molecular sieve, the MFI structure molecular sieve component is the first MFI structure molecular sieve and/or the second MFI structure molecular sieve, wherein,

The second Y-type molecular sieve is DASY molecular sieve containing rare earth;

In the third Y-type molecular sieve, the _{rare earth content calculated as rare earth oxide is 12-16% by weight, and the phosphorus content calculated as P2O5 is} 0.5-7% by weight. In the ³¹ P MAS NMR spectrum of the molecular sieve, chemical The peak area of the resonance signal with a shift of -14 ± 2ppm and -23 ± 2ppm accounts for more than 85% of the total peak area. In the ²⁷ Al MAS NMR spectrum of the molecular sieve, the peak area of the resonance signal with a chemical shift of 0 ± 2ppm accounts for more than 85% of the total peak area. The percentage of area is greater than 20%;

The expression of the anhydrous chemical composition in terms of the molar ratio of oxides in the first MFI molecular sieve is: (0.01-0.25)RE ₂ O ₃ ·(0.005-0.02)Na ₂ O·Al ₂ O ₃ ·(0.2 -1.0)P ₂ O ₅ ·(35-120)SiO ₂ , the adsorption weight ratio of the molecular sieve to n-hexane and cyclohexane is 4-5;

The anhydrous chemical composition expression of the second MFI structural molecular sieve in terms of oxide weight ratio is: (0-0.3)Na ₂ O·(0.5-5.5)Al ₂ O ₃ ·(13-10)P ₂ O ₅ ·(0.7-15)M1 _x O _y ·(0.01-5)M2 _m O _n ·(70-97)SiO ₂ , where M1 is Fe, Co or Ni, x represents the atomic number of M1, and y represents the satisfaction of M1 The number of oxygen required for the oxidation state, M2 is selected from Zn, Mn, Ga or Sn, m represents the number of atoms of M2, and n represents the number of oxygen required to meet the oxidation state of M2.

According to the preparation method of the catalytic cracking catalyst for alkali nitrogen resistance and high yield of liquefied gas provided by the present invention, in step (2), the cracking active component, mesoporous silica-alumina material, clay and binder are mixed and beaten, and the subsequent Spray drying, washing, filtering and drying, the implementation methods of these operations can be implemented by conventional methods, and their specific implementation methods are described in detail in patent applications CN1916166A, CN1362472A, CN1727442A, CN1132898C, CN1727445A and CN1098130A, It is hereby incorporated into the present invention for reference.

According to the method provided by the present invention, in step (2), on a dry basis, the weight of the added amount of the cracking active component, the mesoporous silica-alumina material, the clay and the binder The ratio can be (10-70): (1-20): (10-70): (10-60), preferably (10-45): (2-15): (20-40): (20- 50). The cracking active component, mesoporous silica-alumina material, clay and binder are the same as those described above.

The present invention will be further described below through embodiment.

In the following examples and comparative examples,

The mesoporous silicon-aluminum material is prepared according to the method of Example 1 in CN 1854258A (SH-SA-1);

The second Y-type molecular sieve is DASY2.0 molecular sieve, produced by Sinopec Catalyst Qilu Branch;

The third Y-type molecular sieve was prepared according to the method of Example 1 in the patent application CN101088917A;

The first molecular sieve with MFI structure was prepared according to the method of Example 1 in the patent application CN1147420A;

The second molecular sieve with MFI structure was prepared according to the method of Example 1 in the patent application CN1611299A;

Aluminum sol is produced by Sinopec Catalyst Qilu Branch, with _{an Al2O3} content of 21.5% by weight;

Kaolin was purchased from Suzhou China Kaolin Company;

Pseudoboehmite was purchased from Shandong Aluminum Plant;

Example 1

This example is used to illustrate the catalytic cracking catalyst provided by the present invention.

(1) Preparation of modified Y-type molecular sieve

Add 5.0 kilograms of NaY molecular sieves on a dry basis (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio (SiO ₂ /Al ₂ O ₃ molar ratio) 5.2) and 4 kilograms of deionized water in the reactor, vigorously stir Slowly add 4.0 liters of rare earth chloride solution (provided by Qilu Catalyst Factory, RE ₂ O ₃ content 222.5 g/l), adjust the pH of the system to 3.5 with 4% by weight dilute hydrochloric acid, heat up to 90°C and stir for 1.5 hours, filter , washed and dried; then roasted at 650°C for 2 hours in a 100% water vapor atmosphere to obtain "cross-baked" rare earth sodium Y, which is recorded as modified molecular sieve ABY-1A.

Take 2.0 kg of modified molecular sieve ABY-1A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, and slowly add 0.50 liter of rare earth chloride solution (RE ₂ O ₃ content 222.5 g/liter), 135 gram of Fe(NO ₃ ) ₃ 9H ₂ O, 55 grams of CuCl ₂ .2H ₂ O solid and 48.6 grams of ammonium dihydrogen phosphate, adjust the pH of the system to 3.5 with 4% dilute hydrochloric acid, raise the temperature to 90°C and stir for 1 hour, filter, After washing and drying, the first Y-type molecular sieve of the present invention is obtained, which is recorded as ABY-1.

Fluorescence method (XRF) records that in the ABY-1 sample, the rare earth oxide content is 16.1% by weight, the sodium oxide content is 1.6% by weight, the iron oxide content is 0.75% by weight, the copper oxide content is 0.69% by weight, and the phosphorus pentoxide content is 0.83% by weight.

31P MAS NMR analysis results of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 3.712mmol·g ^-1 , L acid 0.638mmol·g ^-1 , total 4.350mmol·g ^-1 .

31P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 2.054mmol·g ^-1 , L acid 0.582mmol·g ^-1 , total 2.636mmol·g ^-1 .

(2) Preparation of catalytic cracking catalyst

The pseudo-boehmite of 19 weight parts on a dry basis is mixed with deionized water for beating, and adding a concentration of 36% by weight hydrochloric acid for peptization in the obtained slurry, the acid-aluminum ratio (the 36% by weight hydrochloric acid and The weight ratio of pseudo-boehmite on dry basis) is 0.20, the temperature is raised to 65° C. and acidified for 1 hour, and a slurry containing 28 parts by weight of kaolin on a dry basis and 9 parts by weight of aluminum sol on a dry basis are added respectively. And the slurry of the mesoporous silica-alumina material of 8 parts by weight on a dry basis, stirred for 20 minutes, and then added the first Y-type molecular sieve ABY-1 of 23 parts by weight on a dry basis, and A mixed slurry of 5 parts by weight of the second Y-type molecular sieve DASY2.0 and 8 parts by weight of the first MFI molecular sieve on a dry basis, stirred for 30 minutes to obtain a slurry with a solid content of 30% by weight, and then spray-dried Made into microsphere catalyst. The microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ at 60°C ((NH ₄ ) ₂ SO ₄ : microsphere catalyst: _{H 2} O=0.05:1:10) Until the Na ₂ O content is less than 0.25% by weight, rinse with deionized water, filter and then dry at 110° C. to obtain catalytic cracking catalyst C1.

Example 2-7

This example is used to illustrate the catalytic cracking catalyst provided by the present invention.

Prepare catalytic cracking catalyst according to the method of embodiment 1 respectively, difference is, in step (2), mesoporous silicon aluminum material, kaolin, described first Y-type molecular sieve ABY-1, described second Y-type molecular sieve The feed amounts of DASY2.0, the third Y-type molecular sieve, the first MFI structure molecular sieve, the second MFI structure molecular sieve, pseudo-boehmite and aluminum sol on a dry basis are shown in Table 2 below. , when there are multiple molecular sieves in the formula, they are all added in the form of molecular sieve mixed slurry, and the feeding amount of each component is in parts by weight, so as to prepare catalytic cracking catalysts C2-C7 respectively.

Table 2

Comparative example 1

(1) This comparative example is REY prepared according to the method described in patent CN1733362.

Add dry base 3.5 kilograms of NaY molecular sieves (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 20 kilograms of deionized waters in the reactor, add 1.46 liters of rare earth chloride solution (Qilu Catalyst Factory) wherein to it again provided, RE ₂ O ₃ content 222.5 g/L), stirred at 60°C for 5 minutes, adjusted the pH of the system to 3.5-5.5 with hydrochloric acid, continued to stir for 1 hour, added 0.4 kg of ammonia water, stirred for 5 minutes, filtered and washed, dried Roasting furnace, roasting at 600°C for 1.5 hours under water vapor with a weight space velocity of 0.2: ^-1 , then washing with 90°C ammonium chloride solution for 10 minutes according to the ratio of molecular sieve:ammonium chloride:water=1:0.1:10, and drying A comparative molecular sieve DBY was obtained.

Fluorescence method (XRF) measured that the rare earth oxide content in the DBY sample was 16.2% by weight, and the sodium oxide content was 1.6% by weight.

³¹ P MAS NMR analysis results of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 3.657mmol·g ^-1 , L acid 0.574mmol·g ^-1 , total 4.231mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 1.700mmol·g ^-1 , L acid 0.567mmol·g ^-1 , total 2.267mmol·g ^-1 .

(2) Preparation of catalytic cracking catalyst

The catalytic cracking catalyst was prepared according to the method of step (2) in Example 2, except that the DBY was used instead of the first Y-type molecular sieve ABY-1 to obtain the catalytic cracking catalyst DC1.

Comparative example 2-3

The catalytic cracking catalyst was prepared according to the method of Comparative Example 1 respectively, and the difference was that in step (2), mesoporous silica-alumina material, kaolin, DBY molecular sieve, the second Y-type molecular sieve DASY2.0, the third The feed amounts of Y-type molecular sieve, the first MFI structure molecular sieve, the second MFI structure molecular sieve, pseudo-boehmite and aluminum sol are shown in Table 3 below, wherein the feed amount of each component All are in parts by weight, so as to prepare catalytic cracking catalysts DC2-DC3 respectively.

table 3

Example 8

This example is used to illustrate the catalytic cracking catalyst provided by the present invention.

The catalytic cracking catalyst is prepared according to the method of embodiment 3, which is denoted as C8, and the difference is that the preparation method of the modified Y type molecular sieve is:

Add 5.0 kilograms of NaY molecular sieves on a dry basis (provided by Changling Catalyst Factory, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 4 kilograms of deionized water in the reaction kettle, and slowly add 5.12 liters of rare earth chloride solution under vigorous stirring (provided by Qilu Catalyst Factory, RE ₂ O ₃ content 222.5 g/L), use 4% dilute hydrochloric acid to adjust the pH of the system to 3.5, heat up to 90°C and stir for 1.5 hours, filter, wash, and dry; then at 650°C, 100% Calcined under water vapor atmosphere for 2 hours, the "cross-roasted" rare earth sodium Y was obtained, which was recorded as modified molecular sieve ABY-2A.

Take 2.0 kg of modified molecular sieve ABY-2A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 1.44 liters of rare earth chloride solution, 210 g of Fe(NO ₃ ) ₃ 9H ₂ O under vigorous stirring For the solid, use 4% by weight dilute hydrochloric acid to adjust the pH of the system to 3.5, raise the temperature to 90° C. and stir for 1 hour, filter, wash, and dry to obtain the first Y-type molecular sieve of the present invention, which is designated as ABY-2.

Fluorescence method (XRF) measured that the rare earth oxide content in the ABY-2 sample was 21.2% by weight, the content of sodium oxide was 1.3% by weight, and the content of iron oxide was 2.4% by weight.

³¹ P MAS NMR analysis results of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 5.210mmol·g ^-1 , L acid 1.078mmol·g ^-1 , total 6.288mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 3.159mmol·g ^-1 , L acid 1.063mmol·g ^-1 , total 4.222mmol·g ^-1 .

Example 9

This example is used to illustrate the catalytic cracking catalyst provided by the present invention.

Prepare catalytic cracking catalyst according to the method for embodiment 3, be denoted as C9, difference is, the preparation method of modified Y type molecular sieve is:

Add 5.0 kilograms of NaY molecular sieves on a dry basis (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 4 kilograms of deionized water in the reactor, slowly add 4.32 liters of rare earth chloride solution (Qilu Provided by the catalyst factory, RE ₂ O ₃ content 222.5 g/L), use 4% dilute hydrochloric acid to adjust the pH of the system to 3.5, raise the temperature to 90°C and stir for 1.5 hours, filter, wash, and dry; then bake at 550°C for 2 hours, The "Jiaojiayi" rare earth sodium Y was obtained, which was recorded as modified molecular sieve ABY-5A.

Take 2.0 kg of modified molecular sieve ABY-5A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 0.55 liter of rare earth chloride, 40 g of Fe(NO ₃ ) ₃ 9H ₂ O solid under vigorous stirring , 110 grams of CuCl ₂ 2H ₂ O solid, 100 grams of ammonium chloride, adjust the system pH=3.5 with 4% by weight dilute hydrochloric acid, heat up to 90°C and stir for 1 hour, filter, wash, and dry to obtain the present invention. Modified Y molecular sieve, recorded as ABY-5.

Fluorescence method (XRF) measured that the rare earth oxide content in the ABY-5 sample was 19.6% by weight, the content of sodium oxide was 1.5% by weight, the content of iron oxide was 0.29% by weight, and the content of copper oxide was 1.48% by weight.

³¹ P MAS NMR analysis results of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 4.471mmol·g ^-1 , L acid 0.863mmol·g ^-1 , total 5.334mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 2.163mmol·g ^-1 , L acid 0.683mmol·g ^-1 , total 2.846mmol·g ^-1 .

Example 10

This example is used to illustrate the catalytic cracking catalyst provided by the present invention.

Prepare catalytic cracking catalyst according to the method for embodiment 3, be denoted as C10, difference is, the preparation method of modified Y type molecular sieve is:

Add 5.0 kilograms of NaY molecular sieves on a dry basis (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 4 kilograms of deionized water in the reactor, slowly add 5.10 liters of rare earth chloride solution (Qilu Provided by the catalyst factory, RE ₂ O ₃ content 222.5 g/L), adjust the pH of the system to 3.5 with 4% dilute hydrochloric acid, stir at 90°C for 1.5 hours, filter, wash, and dry; Calcined under the atmosphere for 2 hours to obtain "cross-roasted" rare earth sodium Y, which is recorded as modified molecular sieve ABY-4A.

Take 2.0 kg of modified molecular sieve ABY-4A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 1.50 liters of rare earth chloride solution, 135 g of Fe(NO3) ₃ 9H ₂ O and 55 grams of CuCl ₂ ·2H ₂ O solid, adjust the pH of the system to 3.5 with 4% (mass) dilute hydrochloric acid, heat up to 90°C and stir for 1 hour, filter, wash, and dry to obtain the first Y-type molecular sieve of the present invention , remember as ABY-4.

Fluorescence method (XRF) measured that the rare earth oxide content in the ABY-4 sample was 22.5% by weight, the content of sodium oxide was 1.1% by weight, the content of iron oxide was 0.79% by weight, and the content of copper oxide was 0.73% by weight.

³¹ P MAS NMR analysis results of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 5.317mmol·g ^-1 , L acid 1.181mmol·g ^-1 , total 6.498mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 3.265mmol·g ^-1 , L acid 1.097mmol·g ^-1 , total 4.362mmol·g ^-1 .

test case 1

The above-mentioned catalytic cracking catalysts C1-C10 and DC1-DC3 were aged at 800°C and 100% steam for 8 hours respectively, and then filled in a small fixed fluidized bed ACE device (purchased from KTI, USA) to evaluate the catalytic cracking catalysts Excellent reaction performance, the filling volume is 9g. Then, under the conditions of a reaction temperature of 530°C, a weight hourly space velocity of 10 h ^-1 , and a catalyst-to-oil ratio (weight) of 6, the catalytic mixed oil shown in Table 4 was used as the feedstock oil and injected into the small fixed fluidized bed The catalytic cracking reaction is carried out in the ACE unit. Analyze the composition of reaction product, and calculate conversion rate according to following formula, result is as shown in table 5 below:

Table 4

table 5

In the above table 5, by comparing Example 2 with Comparative Example 1, Example 3 with Comparative Example 2, and Example 5 with Comparative Example 3, it can be seen that the catalytic cracking catalyst of the present invention is effective against alkali In the process of catalytic cracking treatment of feedstock oil with high content of neutral nitrogen, it shows relatively high catalytic cracking activity, can obtain high conversion rate, especially can obtain high yield of liquefied gas.

Example 11

Prepare catalyst according to the method for embodiment 5, be denoted as C11, difference is that the first Y type molecular sieve preparation method used is as follows:

Add 5.0 kilograms of NaY molecular sieves on a dry basis (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 4 kilograms of deionized water in the reactor, slowly add 4.20 liters of rare earth chloride solution (Qilu Provided by the catalyst factory, RE ₂ O ₃ content 222.5 g/L), use 4% dilute hydrochloric acid to adjust the pH of the system to 3.5, raise the temperature to 90°C and stir for 1.5 hours, filter, wash, and dry; then bake at 550°C for 2 hours, The "Jiaojiayi" rare earth sodium Y was obtained, which was recorded as modified molecular sieve ABY-11A.

Take 2.0 kg of modified molecular sieve ABY-11A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 0.48 liter of rare earth chloride, 125 g of Fe(NO ₃ ) ₃ 9H ₂ O solid under vigorous stirring , 100 grams of ammonium chloride, adjust the pH of the system to 3.5 with 4% dilute hydrochloric acid, heat up to 90° C. and stir for 1 hour, filter, wash, and dry to obtain the modified Y molecular sieve of the present invention, which is recorded as ABY-11.

Fluorescence method (XRF) measured that the rare earth oxide content in the ABY-11 sample was 17.1% by weight, the sodium oxide content was 1.7% by weight, and the iron oxide content was 0.84% by weight.

The results of ³¹ P MAS NMR analysis of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 4.399 mmol·g ^-1 , L acid 0.756 mmol·g ^-1 , total 5.155 mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 2.100mmol·g ^-1 , L acid 0.658mmol·g ^-1 , total 2.758mmol·g ^-1 .

Example 12

Catalyst is prepared according to the method for embodiment 2, is denoted as C12, and difference is that the first Y type molecular sieve preparation method used is as follows:

Add 5.0 kilograms of NaY molecular sieves on a dry basis (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 2 kilograms of deionized water in the reaction kettle, slowly add 3.16 liters of rare earth chloride solution (Qilu Provided by the catalyst factory, RE ₂ O ₃ content 222.5 g/L), adjust the pH of the system to 3.5 with 4% dilute hydrochloric acid, stir at 90°C for 1.5 hours, filter, wash, and dry; Calcined under the atmosphere for 2 hours to obtain "cross-roasted" rare earth sodium Y, which is recorded as modified molecular sieve ABY-12A.

Take 2.0 kg of modified molecular sieve ABY-12A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 1.48 liters of rare earth chloride, 15 g of Fe(NO ₃ ) ₃ 9H ₂ O solid under vigorous stirring , 90 grams of CuCl ₂ 2H ₂ O solids, adjust the pH of the system to 3.5 with 4% dilute hydrochloric acid, heat up to 90°C and stir for 1 hour, filter, wash, and dry to obtain the modified Y molecular sieve of the present invention, denoted as ABY-12.

Fluorescence method (XRF) measured that the rare earth oxide content in the ABY-12 sample was 18.3% by weight, the content of sodium oxide was 1.3% by weight, the content of iron oxide was 0.13% by weight, and the content of copper oxide was 1.03% by weight.

The results of ³¹ P MAS NMR analysis of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 4.459mmol·g ^-1 , L acid 0.859mmol·g ^-1 , total 5.318mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 2.151mmol·g ^-1 , L acid 0.672mmol·g ^-1 , total 2.823mmol·g ^-1 .

Example 13

Add 5.0 kilograms of NaY molecular sieves on a dry basis (Changling Catalyst Factory provides, crystallinity 86%, skeleton silicon-aluminum ratio 5.2) and 4 kilograms of deionized water in the reactor, slowly add 2.50 liters of rare earth chloride solution (Qilu Provided by the catalyst factory, RE ₂ O ₃ content 222.5 g/L), use 4% dilute hydrochloric acid to adjust the pH of the system to 3.5, raise the temperature to 90°C and stir for 1.5 hours, filter, wash, and dry; then bake at 550°C for 2 hours, The rare earth sodium "Jojiaobaked" is obtained, which is recorded as modified molecular sieve ABY-13A.

Take 2.0 kg of modified molecular sieve ABY-13A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 0.48 liter of rare earth chloride, 80 g of Fe(NO ₃ ) ₃ 9H ₂ O solid under vigorous stirring , 100 grams of ammonium chloride, adjust the pH of the system to 3.5 with 4% dilute hydrochloric acid, heat up to 90° C. and stir for 1 hour, filter, wash, and dry to obtain the modified Y molecular sieve of the present invention, which is recorded as ABY-13.

Fluorescence method (XRF) measured that the rare earth oxide content in the ABY-13 sample was 10.2% by weight, the content of sodium oxide was 2.3% by weight, and the content of iron oxide was 0.53% by weight.

³¹ P MAS NMR analysis results of the sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 2.370mmol·g ^-1 , L acid 0.223mmol·g ^-1 , total 2.593mmol·g ^-1 .

³¹ P MAS NMR analysis results of the sample after adsorption of tributylphosphorus oxide (TBPO): B acid 1.025mmol·g ^-1 , L acid 0.218mmol·g ^-1 , total 1.243mmol·g ^-1 .

Comparative example 4

Take 2.0 kg of modified molecular sieve ABY-13A dry basis and put it into the reaction kettle, add 1.6 kg of deionized water, slowly add 0.48 liter of rare earth chloride and 100 g of ammonium chloride under vigorous stirring, and adjust the system with 4% dilute hydrochloric acid pH = 3.5, heated up to 90°C and stirred for 1 hour, filtered, washed, and dried to obtain a comparative molecular sieve, which was designated as DBY-8.

Fluorescence method (XRF) measured that the rare earth oxide content in the DBY-8 sample was 10.2% by weight, and the sodium oxide content was 2.3% by weight.

The results of ³¹ P MAS NMR analysis of the comparative sample after adsorption of trimethylphosphorus oxide (TMPO): B acid 2.311mmol·g ^-1 , L acid 0.235mmol·g ^-1 , total 2.546mmol·g ^-1 .

The results of ³¹ P MAS NMR analysis of the comparative sample after adsorption of tributylphosphorus oxide (TBPO): B acid 0.934mmol·g ^-1 , L acid 0.209mmol·g ^-1 , total 1.143mmol·g ^-1 .

test case 2

Exchange DBY-8 and ABY-13 with NH ₄ Cl for 2-3 times to reduce the Na ₂ O content to below 0.3% by weight, and then aging at 800℃/17h, 100% steam to evaluate light oil microreflection Activity, see "Petrochemical Analysis Method (RIPP Method)", Science Press, 1990. After no addition or addition of 1200 μg/g basic nitrogen compound 2-methylquinoline in the standard gas oil feedstock, the microreaction activity of the samples is listed in Table 6.

Table 6

Claims (11)

1. A cracking catalyst resistant to alkali nitrogen and producing liquefied gas, comprising: 10-70 wt% cracking active component, 1-20 wt% mesoporous silica-alumina material, 10-60 wt% binder and 10-70 wt% clay, wherein the cracking active component includes 70-85% by weight of Y-type molecular sieve and 15-30% by weight of MFI structure molecular sieve, the Y-type molecular sieve includes the first Y-type molecular sieve, wherein, the first Y-type molecular sieve is made of rare earth, iron, copper 1. Phosphorus-modified _Y -type molecular sieve, the rare earth content in the first molecular sieve is 8-23% by weight as rare earth oxide, the iron content is 0.1-3.0% by weight as _Fe2O3 , and the copper content is 0.1-3.0% by weight as CuO 0-3.0% by weight, the phosphorus content is 0-2.0% by weight based on _P2O5 , and the sodium oxide content is 0.1-2.5% by weight; after the first Y-type molecular sieve adsorbs tributylphosphine oxide _, ³¹ P MAS NMR The determined molecular sieve acid content is 1.400-4.500mmol·g ^-1 , and the molecular sieve acid content determined by ³¹ P MAS NMR after the adsorption of trimethylphosphorus oxide is 2.300-6.600 mmol·g ^-1 . 2. according to the cracking catalyst of the anti-alkali nitrogen prolific liquefied gas described in claim 1, it is characterized in that, in the described first Y-type molecular sieve, the rare earth content is 10-20% by weight in terms of rare earth oxide, and the iron content is in the form of Fe ₂ O ₃ is 0.5-2.5 wt%, the copper content is 0.2-1.5 wt% as CuO, and the phosphorus content is 0-1.0 wt% as P ₂ O ₅ . 3. according to the cracking catalyst of anti-alkali nitrogen prolific liquefied gas described in claim 1, it is characterized in that, in the described first Y-type molecular sieve, rare earth content is 14-20 weight % by rare earth oxide, iron content is Fe ₂ O ₃ is 0.6-1.0 wt%, the copper content is 0.5-1.2 wt% as CuO, the phosphorus content is 0-1.0 wt% as P ₂ O ₅ , and the sodium oxide content is 0.1-2.0 wt%. 4. according to the cracking catalyst of anti-alkali and nitrogen prolific liquefied gas described in claim 1, it is characterized in that, described first Y-type molecular sieve is obtained by the method comprising following preparation process: take NaY molecular sieve as raw material, through rare earth exchange And roasting to obtain "cross-baking" RENaY, and then react with rare earth compounds, iron-containing substances, copper-containing substances, phosphorus-containing substances, with or without ammonium salts. 5. according to the cracking catalyst of anti-alkali nitrogen prolific liquefied gas described in claim 4, it is characterized in that, the described process of obtaining " cross-bake " RENaY is that NaY molecular sieve and rare earth compound are in NaY:RE ₂ O ₃ = 1: 0.10-0.25 weight ratio, pH = 2.0-4.5, exchange temperature 25-100°C for 0.3-1.5 hours, filter, wash, filter cake at 400-850°C, 0-100% water vapor Lower roasting for more than 0.3 hours; the process of reacting with rare earth compounds, iron-containing substances, copper-containing substances, phosphorus-containing substances, and or not with ammonium salts is to combine RENaY with rare earth compounds, iron-containing substances, copper-containing substances, and phosphorus-containing The substance, with or without ammonium salt, according to NaY: RE ₂ O ₃ : Fe ₂ O ₃ /CuO: P ₂ O ₅ : ammonium salt = 1: 0.02-0.15: 0.001-0.05: 0-0.04: 0 -0.5 weight ratio, pH=2.0-4.5, react at 20-100°C, then filter and wash. 6. According to the cracking catalyst of claim 1, wherein the anti-alkali nitrogen multi-production liquefied gas is characterized in that, the Y-type molecular sieve comprises 20-100% by weight of the first Y-type molecular sieve and 0-80% by weight The second Y-type molecular sieve and/or the third Y-type molecular sieve; the second Y-type molecular sieve is DASY molecular sieve, and the rare earth content in the third Y-type molecular sieve is 12-16% by weight in terms of rare earth oxides , the phosphorus content based on P ₂ O ₅ is 0.5-7% by weight, in the ³¹ P MAS NMR spectrum of the molecular sieve, the chemical shift is -14 ± 2ppm and -23 ± 2ppm The peak area of the resonance signal accounts for the percentage of the total peak area More than 85%, in the ²⁷ Al MAS NMR spectrum of the molecular sieve, the peak area of the resonance signal with a chemical shift of 0±2ppm accounts for more than 20% of the total peak area. 7. according to the cracking catalyst of anti-alkali nitrogen prolific liquefied gas described in claim 6, it is characterized in that, in the ³¹ P MAS NMR spectrum of described third Y-type molecular sieve, chemical shift is-14 ± 2ppm and-23 ± 2ppm The peak area of the 2ppm resonance signal accounts for more than 90% of the total peak area, and the unit cell constant is 8. according to the cracking catalyst of anti-alkali nitrogen prolific liquefied gas described in claim 1, it is characterized in that, described MFI structure molecular sieve is the first MFI structure molecular sieve and/or the second MFI structure molecular sieve, described first Molecular sieve with MFI structure, the anhydrous chemical composition expression in terms of molar ratio of oxides is: (0.01-0.25)RE ₂ O ₃ ·(0.005-0.02)Na ₂ O ·Al ₂ O ₃ ·(0.2-1.0)P ₂ O ₅ ·(35-120)SiO ₂ , the molecular sieve has an adsorption weight ratio of 4-5 to n-hexane and cyclohexane; the anhydrous chemical composition of the second MFI structure molecular sieve is expressed in terms of oxide weight ratio The formula is: (0-0.3) Na ₂ O · (0.5-5.5) Al ₂ O ₃ · (1.3-10) P ₂ O ₅ · (0.7-15) M1 _x O _y · (0.01-5) M2 _m O _n ·(70-97)SiO ₂ , where M1 is Fe, Co or Ni, x represents the number of atoms of M1, y represents the number of oxygen required to satisfy the oxidation state of M1, and M2 is selected from Zn, Mn, Ga or Sn , m represents the number of atoms of M2, and n represents the number of oxygen required to satisfy the oxidation state of M2. 9. according to the cracking catalyst of anti-alkali nitrogen prolific liquefied gas described in claim 1, it is characterized in that, described mesoporous silicon-aluminum material has the phase structure of pseudo-boehmite, anhydrous by oxide weight The chemical expression is: (0-0.3)Na ₂ O·(40-90)Al ₂ O ₃ ·(10-60)SiO ₂ , the average pore diameter is 8-20nm, the most probable pore diameter is 5-15nm, the ratio The surface area is 200-400m ² /g, and the pore volume is 0.5-2.0ml/g. 10. The cracking catalyst for resisting alkali nitrogen and producing liquefied gas according to claim 1, characterized in that, the content of the cracking active component is 10-45% by weight on a dry basis, and the mesoporous silicon-aluminum material The content of the clay is 2-15% by weight on a dry basis, the content of the clay is 15-40% by weight on a dry basis, and the content of the binder is 20-50% by weight on a dry basis. 11. the preparation method of the cracking catalyst of the anti-alkali nitrogen prolific liquefied gas described in any one of claim 1-10, comprises cracking active component, mesoporous material, clay and binding agent beating, spray drying, washing, Filtration and drying steps.