CN1224456C - Hydrocarbon cracking catalyst and preparing method thereof - Google Patents

Abstract

The present invention relates to a cracking catalyst for hydrocarbons, which comprises a zeolite composition and a substrate material, wherein the zeolite composition contains 50 to 99.5 wt% of zeolite, 0.1 to 10 wt% of fluorine, silicon component and phosphorus; the zeolite composition is used as the reference, the content of SiO2 is from 0.1 to 20 wt%, and the content of P2O5 is from 0.1 to 20 wt%. The catalyst has the advantages of high cracking activity and high octane number of a gasoline product.

Description

A kind of hydrocarbon cracking catalyzer and preparation method thereof

Technical field

The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof.

Background technology

Hydrocarbon cracking catalyzer generally contains zeolite and a kind of host material.Described host material is selected from heat-resistant inorganic oxide and/or clay.In order to improve the performance of Cracking catalyst aspect, also often contain a kind of zeolite compositions.Various zeolite compositions emerge in an endless stream with the Cracking catalyst that contains zeolite compositions in the prior art for this reason.Phosphorous or fluorine-containing zeolite compositions and the Cracking catalyst that contains this zeolite compositions promptly are examples wherein.

EP 0,397, and 183 disclose a kind of composition, and said composition contains Na ₂O content is that 2-5 weight % is through the NaY of ion-exchange zeolite with P ₂O ₅Meter, the phosphorus of 0.1-4.0 weight %.The preparation method of said composition comprises the NaY zeolite is carried out ion-exchange, obtains Na ₂O content be 1-5 weight % through the NaY of ion-exchange zeolite; To reclaim with P through the reactant aqueous solution of the NaY of ion-exchange zeolite and a kind of phosphorus compound ₂O ₅Meter, phosphorus content is the product that contains y-type zeolite of 0.1-4.0 weight %.Wherein, described phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and sodium dihydrogen phosphate.Said composition can form phosphorous overstable gamma zeolite through hydrothermal treatment consists, as the active component of Cracking catalyst.

US4,839,319 disclose a kind of catalyst, and this catalyst contains a kind of nonzeolite inorganic oxide matrix and a kind of overstable gamma zeolite, and described overstable gamma zeolite makes the compound phosphorus of going up effective dose on the zeolite by contacting time enough with a kind of phosphorus compound.Described phosphorus compound is selected from one group that is made up of phosphoric acid, phosphorous acid, phosphate and phosphite.This catalyst has lower coking yield as hydrocarbon cracking catalyzer.

US5,110,776 disclose a kind of preparation method who contains the zeolite catalysis Cracking catalyst, and this method comprises that (a) handles zeolite with a kind of phosphatic aqueous solution, makes Zeolite modifying, obtains a kind of aqueous slurry; (b) described aqueous slurry is directly mixed with a kind of matrix precursor, spray-drying obtains catalyst.The catalyst that contains phosphorus-modified zeolite with this method preparation has abrasion resistance preferably, and when the catalytically crack hydrocarbons raw material, the gasoline that obtains has higher octane number.

CN 1210509A discloses a kind of method of producing alkylbenzene, and this method is included in fluorine-containing modenite and exists down, under the condition that generates monoalkyl benzene, benzene is contacted with the alkene that contains 8-30 the carbon atom of having an appointment.Described modenite contains the fluorine of the 0.1-4 weight % that has an appointment.This fluorine-containing modenite is with SiO ₂With Al ₂O ₃Mol ratio is that the modenite of 10-100 contacts with aqueous hydrogen fluoride solution and prepares.

US 4,388, and 178 disclose a kind of cracking method of petroleum hydrocarbon raw material, and this method is included under the cracking hydrocarbon condition and under 850-950 the temperature, a kind of petroleum hydrocarbon raw material is contacted with a kind of zeolitic cracking catalyst.This catalyst is made up of y-type zeolite and a kind of silica one alumina host of at least 90 weight %, and described catalyst also contains the fluorine of 0.1-5 weight %.The yield that uses this catalyst can increase engine fuel also can improve octane number.

Summary of the invention

The purpose of this invention is to provide a kind of new higher cracking activity that has, and gasoline fraction has more high-octane hydrocarbon cracking catalyzer and preparation method thereof in the crackate.

Catalyst provided by the invention contains a kind of zeolite compositions and a kind of host material, wherein, described zeolite compositions contains zeolite, fluorine, silicon components and phosphorus, total amount with zeolite compositions is a benchmark, the content of zeolite is 50-99.5 weight %, in element, the content of fluorine is 0.1-10 weight %, with SiO ₂Meter, the content of silicon components is 0.1-20 weight %, with P ₂O ₅Meter, the content of phosphorus is 0.1-20 weight %.

Preparation of catalysts method provided by the invention comprises mixes making beating with zeolite compositions with the precursor and the deionized water of host material and/or host material, dry, wherein, described zeolite compositions contains zeolite, fluorine, silicon components and phosphorus, total amount with zeolite compositions is a benchmark, and the content of zeolite is 50-99.5 weight %, in element fluorine, the content of fluorine is 0.1-10 weight %, with SiO ₂Meter, the content of silicon components is 0.1-20 weight %, with P ₂O ₅Meter, the content of phosphorus is 0.1-20 weight %; The preparation method of described zeolite compositions comprises zeolite is mixed jointly or step by step with the fluorine compounds aqueous solution, phosphorous compound aqueous solution and silicon compound, or with the fluorine compounds aqueous solution, phosphorous compound aqueous solution, the silicon compound aqueous solution common or step impregnation zeolite, the each mixing or dipping back drying, roasting or not roasting mix or dipping back roasting for the last time.

Because the contained zeolite compositions of catalyst provided by the invention has higher heat endurance, higher hydrocarbon activity of conversion, isomerization activity and hydrogen transfer activity, the catalyst provided by the invention that contains this zeolite compositions has the cracking activity higher than prior art, and gasoline fraction has higher octane number in the crackate.For example, be 28.6 weight % with alumina content provided by the invention, kaolin content is 42.8 weight %, (with the zeolite compositions is benchmark to zeolite compositions, and the HY zeolite content is 92.4 weight %, and in fluorine element, fluorine content is 1.3 weight %, with SiO ₂Meter, silicon components content is 2.1 weight %, with P ₂O ₅Meter, phosphorus content is 4.2 weight %) content is that the catalyst of 28.6 weight % is at 800 ℃, with 100% steam after aging 4 hours, in reaction temperature is 482 ℃, weight (hourly) space velocity (WHSV) is 16 hours-1, and the agent weight of oil is than being under 4 the condition, is that 227-475 ℃ decompressed wax oil carries out catalytic cracking to boiling range, conversion ratio is up to 79 weight %, and the research octane number (RON) of gasoline product (RON) is up to 90.3.And adopt other constituent content identical, and just zeolite compositions is respectively the HY zeolite, the HY zeolite content is 98.7 weight %, and in element fluorine, fluorine content is that zeolite reference composition and the HY zeolite content of 1.3 weight % is 95.8 weight %, with P ₂O ₅, when phosphorus content was the catalyst of reference zeolite compositions of 4.2 weight %, conversion ratio had only 70 weight %, 73 weight % and 74 weight % respectively, and the octane number of gasoline product has only 87.8,88.5 and 88.6 respectively.

The specific embodiment

According to catalyst provided by the invention, be benchmark with the total amount of described zeolite compositions, the content of zeolite is preferably 70-99 weight %, and in element fluorine, the content of fluorine is preferably 0.1-5 weight %, with SiO ₂Meter, the content of silicon components is preferably 0.2-10 weight %, with P ₂O ₅Meter, phosphorus content is preferably 0.2-15 weight %.

In described zeolite compositions, described fluorine is with the compound of fluorine, as the form existence of fluoride and/or fluosilicate.Silicon components is with the compound of silicon, exists as the form of oxide, silicate and/or the fluosilicate of silicon.Because the fluorine in the zeolite compositions is easy and the framework aluminum reaction of zeolite, make the zeolite dealuminzation, room after staying dealuminzation on the zeolite, silicon components in the zeolite compositions of the present invention can be filled up the room of taking out behind the aluminium in preparation process, thereby the part in the silicon components may form the framework silicon of zeolite.Described phosphorus is with phosphorus compound, as the oxide and/or the existence of phosphatic form of phosphorus.

Zeolite in the described zeolite compositions is selected from one or more in manually synthetic and natural macropore, mesopore and the aperture aluminosilicate zeolite.

Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujasite, L zeolite, Beta zeolite, omega zeolite, modenite, the ZSM-18 zeolite one or more, y-type zeolite particularly contains in the y-type zeolite (abbreviating REY or REHY as), overstable gamma zeolite (abbreviating USY as), the overstable gamma zeolite (abbreviating REUSY as) that contains rare earth, Beta zeolite, modenite of rare earth one or more.

Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as have in the zeolite (as the ZSM-5 zeolite, the zeolite of the disclosed MFI of the having structure of CN1194181A) of MFI structure, the zeolite with the MFI structure ZSM-5 zeolite of rare earth (as contain) that contains rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more.

Described pore zeolite refers to have the zeolite less than the cavernous structure of 0.56 nano-rings opening, as ZSM-34 zeolite and/or erionite.

In preferred large pore zeolite of described zeolite and the mesopore zeolite one or more, preferred especially y-type zeolite, contain y-type zeolite, the overstable gamma zeolite of rare earth, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the modenite one or more.Sodium oxide content is not particularly limited in the described zeolite, and preferred sodium oxide content is less than 1 weight %.

Described zeolite compositions and the host material content in catalyst is conventional content.In general, with the catalyst total amount is benchmark, the content of described zeolite compositions is 1-99 weight %, the content of host material is 1-99 weight %, and under the preferable case, the content of described zeolite compositions is 10-70 weight %, the content of host material is 30-90 weight %, more under the preferable case, the content of described zeolite compositions is 10-60 weight %, and the content of host material is 40-90 weight %.

Described host material is selected from one or more in the Cracking catalyst host material commonly used, as in heat-resistant inorganic oxide and the clay one or more.

Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of Cracking catalyst matrix components and/or binder component one or more, as in aluminium oxide, silica, amorphous aluminum silicide, zirconia, titanium oxide, alkaline earth oxide, the boron oxide one or more, one or more in preferred aluminium oxide, silica and the amorphous aluminum silicide.

Described clay is selected from as in the clay of Cracking catalyst matrix components one or more, as in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more, preferred kaolin.

According to embodiment preferred of the present invention, catalyst provided by the invention contains above-mentioned zeolite compositions, the host material aluminium oxide, contain or do not contain the host material clay, with the catalyst total amount is benchmark, the content of zeolite compositions is 10-70 weight %, and the content of aluminium oxide is 5-60 weight %, and the content of clay is 0-75 weight %.Under the preferable case, the content of zeolite compositions is 10-60 weight %, and alumina content is 10-50 weight %, and clay content is 10-60 weight %.Described clay is preferably kaolin, in preferred macropore of zeolite in the described zeolite compositions and the mesopore zeolite one or more, be preferably y-type zeolite especially, contain y-type zeolite, the overstable gamma zeolite of rare earth, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the modenite one or more.

Catalyst provided by the invention can also contain a kind of zeolite that is not included in the above-mentioned zeolite compositions except that containing above-mentioned zeolite compositions and host material, be called the independent component zeolite here.Described independent component zeolite is selected from as in the zeolite of active component of cracking catalyst one or more, be preferably in large pore zeolite and the mesopore zeolite one or more, y-type zeolite more preferably, the y-type zeolite that contains rare earth, overstable gamma zeolite, the overstable gamma zeolite that contains rare earth, the Beta zeolite, zeolite with MFI structure, the zeolite that contains rare earth with MFI structure, in the modenite one or more, particularly have the zeolite of MFI structure and/or contain the zeolite with MFI structure of rare earth. with the catalyst total amount is benchmark, the content of described independent component zeolite is 0-40 weight %, is preferably 0-30 weight %.

According to Preparation of catalysts method provided by the invention, described mixed process with zeolite and the fluorine compounds aqueous solution, phosphorous compound aqueous solution and the silicon compound aqueous solution, perhaps can carry out simultaneously or step by step, the sequencing that mixes or flood is not particularly limited with the process of the fluorine compounds aqueous solution, the silicon compound aqueous solution and phosphorous compound aqueous solution dipping zeolite.Under the preferred situation, earlier with zeolite and silicon compound aqueous solution or elder generation's silicon compound aqueous solution dipping zeolite, dry, roasting or not roasting, again zeolite is mixed simultaneously or step by step with the phosphorous compound aqueous solution and the fluorine compounds aqueous solution, perhaps use the phosphorous compound aqueous solution and fluorine compounds aqueous solution while or step impregnation zeolite, mix or dipping back drying at every turn, roasting or not roasting mix or the dry and roasting in dipping back for the last time.

The temperature of described drying can be preferably 100-250 ℃ from room temperature to 300 ℃, and the temperature of roasting is greater than 300 ℃ to 700 ℃, is preferably 400-650 ℃, and the time of roasting is more than 0.5 hour, is preferably 0.5-20 hour, more preferably 0.5-10 hour.

Described fluorine compounds are selected from one or more in water-soluble fluorine compounds, as hydrogen fluoride, alkali-metal fluoride, one or more in the ammonium fluoride.The concentration of the fluorine compounds aqueous solution can be any possible concentration, as long as mixes afterwards with zeolite or after flooding zeolite, the fluorine that can introduce 0.1-10 weight % in final zeolite compositions gets final product.If the concentration of the fluorine compounds aqueous solution is higher, can only carry out single-steeping or mixing, can introduce the fluorine of q.s.If the fluorine compounds aqueous solution is lower, then can repeatedly flood or mix, dipping or mixing back are dry at every turn, to introduce the fluorine of q.s.

Described phosphorus compound is selected from one or more in water-soluble phosphorus compound, as in phosphoric acid, phosphate, phosphorous acid and the phosphite one or more, and one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate (ADP) particularly.The concentration of phosphorous compound aqueous solution can be any possible concentration, as long as mixes afterwards with zeolite or after flooding zeolite, can introduce with P in final zeolite compositions ₂O ₅Meter, the phosphorus of 0.1-10 weight % gets final product.If the concentration of phosphorous compound aqueous solution is higher, can only carry out mixed once or dipping, just can introduce the phosphorus of q.s.If the concentration of phosphorous compound aqueous solution is lower, then can repeatedly flood or mix, dipping or mixing back are dry at every turn, to introduce the phosphorus of q.s.

Described silicon compound is selected from one or more in water-soluble silicon compound, as silicon tetrachloride, tetramethoxy-silicane Si (OCH ₃) ₄, tetraethoxy-silicane Si (OC ₂H ₅) ₄In one or more.The concentration of the silicon compound aqueous solution can be any possible concentration, as long as after mixing with zeolite or flooding zeolite, can introduce with SiO in final zeolite compositions ₂Meter, the silicon components of 0.1-20 weight % gets final product.If the concentration of the silicon compound aqueous solution is higher, can only carry out the silicon components that mixed once or dipping can be introduced q.s.If the concentration of the silicon compound aqueous solution is lower, then can repeatedly mix or flood, until the silicon components of introducing q.s, dipping or mixing back are dry at every turn.

The method of zeolite compositions being mixed the drying after pulling an oar with the precursor of host material and/or host material is conventionally known to one of skill in the art, described drying can adopt the method for existing various dryings, as dry, method such as oven dry, forced air drying, spray-drying, the method for preferably spray drying.Dry temperature can be preferably 50-250 ℃ from room temperature to 300 ℃.If also contain described independent component zeolite in the catalyst, can when making beating, add in the lump.

When zeolite compositions is mixed making beating with the precursor of host material and/or host material, the consumption of each component preferably makes final catalyst contain, with the catalyst total amount is benchmark, 1-99 weight %, preferred 10-70 weight %, the more preferably described zeolite compositions of 10-60 weight %, 1-99 weight %, preferred 30-90 weight %, the more preferably host material of 40-90 weight %.

Wherein, the precursor of described host material refers in catalyst preparation process, can form the material of described host material, can be selected from any hydrated alumina (as boehmite), aluminium colloidal sol etc. as the precursor of aluminium oxide.The precursor of silica can be selected from silicon solution, silicon gel, waterglass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, silica-alumina gel.The precursor of other heat-resistant inorganic oxides can be selected from their hydroxide separately.

Catalyst provided by the invention can be used for the various petroleum distillates of catalytic cracking, and to produce low-molecular-weight cut, particularly production has high-octane gasoline.Described petroleum distillate can be selected from crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane light/in heavily de-oiling, wax tailings and the coal liquefaction product one or more.

When using catalyst provided by the invention that petroleum distillate is carried out catalytic cracking, reaction condition is conventional catalytic cracking reaction condition, is 400-600 ℃ as reaction temperature, is preferably 450-550 ℃, and weight (hourly) space velocity (WHSV) is 10-120 hour ^-1, be preferably 10-80 hour ^-1, the agent weight of oil is preferably 3-15 than for 1-20.

The following examples will the present invention will be further described.

Example 1

This example illustrates zeolite compositions of the present invention and preparation method thereof.

(1) (lattice constant is 2.462 nanometers, Na with 10 kilograms of NaY zeolites ₂O content is 12.4 weight %, the Zhou village catalyst plant is produced) being 10 weight % with 10 liters of concentration, ammonium sulfate solution mixes, under agitation, carried out ion-exchange 2 hours in 80 ℃, filter, spend deionised water filter cake to sulfate radical-free ion and be detected, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours, (lattice constant is 2.458 nanometers, Na to obtain the HY zeolite ₂O content is 0.5 weight %).Wherein, lattice constant adopts X-ray diffraction method to measure Na ₂O content adopts aas determination.

(2) with 10 kilograms in the above-mentioned HY zeolite that obtains and 6.5 kilograms of SiCl ₄Content is that the silicon tetrachloride aqueous solution of 5 weight % is even, filters, and 120 ℃ of oven dry obtain containing the HY zeolite of silicon components.

(3) be 0.05 mol with 10 kilograms of HY zeolites that contain silicon components that obtain and 30 liters of ammonium fluoride concentration, ammonium hydrogen phosphate concentration is that the ammonium fluoride of 0.1 mol and the mixed aqueous solution of ammonium hydrogen phosphate mix, filter, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain zeolite compositions Z1 of the present invention.The composition of Z1 is listed in the table 5.

Wherein, in the zeolite compositions, the content of phosphorus, fluorine, silicon adopts the x-ray fluorescence spectrometry method to measure.

Example 2-7

Following example illustrates zeolite compositions of the present invention and preparation method thereof.

Step by (2) in the example 1 and (3) prepares zeolite compositions, the kind of the kind of different is zeolite and consumption, silicon compound, phosphorus compound, the fluorine compounds aqueous solution is different with consumption, the temperature and time of roasting is also different, obtains zeolite compositions Z2-Z7 of the present invention.Table 1 has provided the source of used zeolite, zeolite, wherein contained components contents and cell parameter.Table 2 has provided kind and the consumption and the silicon compound kind of zeolite, the concentration of the silicon compound aqueous solution and consumption.Table 3 has provided the kind of phosphorus compound and fluorine compounds and the concentration and the consumption of the aqueous solution thereof.Table 4 has provided sintering temperature and time.Table 5 has provided the composition of zeolite compositions Z2-Z7.

Comparative Examples 1-2

Following Comparative Examples explanation reference zeolite compositions and preparation method thereof.

Method by example 2 prepares zeolite compositions, different is not with the step of silicon aqueous solution, the fluorine compounds aqueous solution or phosphorous compound aqueous solution with identical type and concentration replaces fluorine compounds and phosphorus compound mixed aqueous solution respectively, the consumption of the fluorine compounds aqueous solution or phosphorous compound aqueous solution is respectively 15 liters and 15 liters, obtains reference zeolite compositions ZB1 and ZB2.The composition of ZB1 and ZB2 is listed in the table 5.

Table 1

Zeolite type	Lattice constant, nanometer	Na 2O content, weight %	Rare earth oxide content, weight %	The source
					HY	2.458	0.5	-	In the example (1)
REHY	2.447	0.9	3.6 1.	The Zhou village catalyst plant
					REY	2.453	0.7	19.5 2.	The Zhou village catalyst plant
USY	2.440	0.82	-	The Zhou village catalyst plant
					REUSY	2.444	0.6	1.5 3.	The Zhou village catalyst plant
Annotate: 1. wherein, lanthana content is 2.57 weight %, and cerium oxide content is 0.64 weight %, and other rare earth oxide content is 0.39 weight %.2. wherein, lanthana content is 13.7 weight %, and oxidation Cerium content is 3.4 weight %, and other rare earth oxide content is 2.4 weight %.3. wherein, lanthana content is 1.1 weight %, and cerium oxide content is 0.3 weight %.Other rare earth oxide content is 0.1 weight %.

Table 2

Example number	Zeolite		The silicon compound aqueous solution
						Kind	Consumption, kilogram	The silicon compound kind	Concentration of aqueous solution, weight %	Amount of aqueous solution used, kilogram
	2	HY	10	SiCl 4	6.0						18.5
3						REHY	10	SiCl 4	4.0	15
	4	REY	10	SiCl 4	2.5						20
5						USY	10	SiCl 4	8.0	16
	6	REUSY	10	SiCl 4	3.0						22.5
7						HY	10	Si(OCH 3) 4	10	25

Table 3

Example number	Fluorine compounds and phosphorus compound mixed aqueous solution
						The fluorine compounds kind	Fluorine compounds concentration, mol	The phosphorus compound kind	Phosphorus compound concentration, mol	The mixed aqueous solution consumption rises
	2	NH 4F	0.5	NH 4H 2P0 4	0.5						16.5
3						HF	0.01	(NH 4) 3PO 4	0.05	100
	4	NH 4F	0.1	NH 4H 2PO 4	0.2						30
5						NH 4F	0.4	(NH 4) 3PO 4	0.15	20
	6	NH 4F	0.2	(NH 4) 3PO 4	0.15						22.5
7						NH 4F	1.0	(NH 4) 3PO 4	1.0	18

Table 4

Example number	Sintering temperature, ℃	Roasting time, hour
			2	480	8
3	520	3
			4	500	4
5	530	1
			6	500	2
7	500	3

Table 5

Example number	Zeolite compositions	Fluorine content, weight %	SiO 2Content, weight %	P 2O 5Content, weight %	Zeolite type	Zeolite content, weight %
							1	Z1	0.14	1.1	1.2	HY	97.56
2	Z2	1.3	2.1	4.2	HY	92.4
							Comparative Examples 1	ZB1	1.3	-	-	HY	98.7
Comparative Examples 2	ZB2	-	-	4.2	HY	95.8
							3	Z3	0.12	1.2	3.6	REHY	95.08
4	Z4	0.4	1.3	3.9	REY	94.4
							5	Z5	1.4	2.6	1.2	USY	94.8
6	Z6	0.26	1.9	2.0	REUSY	95.84
							7	Z7	3.1	7.2	10.3	HY	79.4

Example 8

This example illustrates the heat endurance of zeolite compositions of the present invention.

In the sample cell of U.S. TA company's T A5000-DSC2910 differential thermal analyzer, put into 200 milligrams zeolite compositions Z2 of the present invention, under the purging of high pure nitrogen (flow of high pure nitrogen is 90 ml/min), temperature in the sample cell is warming up to 1200 ℃ with 10 ℃/minute heating rate from room temperature, record the lattice avalanche temperature of Z2, the results are shown in Table 6.

Comparative Examples 3-5

The heat endurance of following Comparative Examples explanation reference zeolite compositions.

Measure the HY zeolite of (1) preparation in the example 1, the lattice avalanche temperature of reference zeolite compositions ZB1, ZB2 respectively by the method for example 8, the results are shown in Table 6.

Table 6

Example number	Zeolite compositions	Lattice avalanche temperature, ℃
			8	Z2	1058
Comparative Examples 3	HY	1029
			Comparative Examples 4	ZB1	1034
Comparative Examples 5	ZB2	1045

The result of table 6 shows that with the HY zeolite, the only phosphorous reference zeolite compositions that the only fluorine-containing reference zeolite compositions that fluorine content is identical is identical with phosphorus content is compared, and the lattice avalanche temperature of zeolite compositions of the present invention all obviously improves.This illustrates that zeolite compositions of the present invention has higher heat endurance.

Example 9-15

Following example illustrates the catalytic performance of zeolite compositions of the present invention.

In the reactor of pulse micro-inverse device, the particle diameter of packing into is the zeolite compositions Z1-Z7 of the present invention of the example 1-7 preparation of 0.25-0.44 millimeter, be under 400 ℃ the condition in reaction temperature, feed ortho-xylene with pulse mode, the ortho-xylene consumption is 0.2 microlitre, carrier gas is a nitrogen, and carrier gas flux is 22 ml/min.With the composition of gas chromatographic analysis product, the results are shown in Table 7.

Wherein, ortho-xylene percetage by weight in conversion ratio=100%-product; Isomerization rate=100% * [1-(in the product in ortho-xylene molar fraction/product total xylene molar fraction)]/(1-α); Toluene molar fraction * 100% in disproportionation rate=product; Hydrogen transfer activity=isomerization rate/disproportionation rate; Wherein α is the molar fraction of ortho-xylene when xylene isomerization reaction reaches thermodynamical equilibrium under the reaction temperature, is approximately equal to 0.25 for 400 ℃ in reaction temperature.

Comparative Examples 6-8

The following Comparative Examples explanation HY zeolite and the catalytic performance of reference zeolite compositions.

The method of pressing example 10 is estimated the catalytic performance of zeolite compositions, and different is, uses the HY zeolite of (1) preparation in the example 1 respectively, and reference zeolite compositions ZB1 and ZB2 replace zeolite compositions Z2 of the present invention.Reaction result is listed in the table 7.

Table 7

Example number	Zeolite compositions	Conversion ratio, weight %	Isomerization rate, %	The disproportionation rate, %	Hydrogen transfer activity
						9	Z1	63.2	66.0	13.9	4.74
10	Z2	66.81	70.1	16.6	4.22
						Comparative Examples 6	HY	32.76	31.07	8.31	3.73
Comparative Examples 7	ZB1	52.67	53.51	13.3	4.02
						Comparative Examples 8	ZB2	56.7	60.4	15.58	3.88
11	Z3	71.5	73.63	17.07	4.31
						12	Z4	72.5	75.8	17.2	4.41
13	Z5	70.6	72.1	16.9	4.27
						14	Z6	69.76	71.9	16.4	4.38
15	Z7	60.4	62.3	12.8	4.87

From the result of table 7 as can be seen, with the existing zeolite compositions with same amount phosphorus or fluorine with without the zeolite facies ratio of modification, zeolite compositions of the present invention has higher hydrocarbon activity of conversion, higher isomerization rate and the hydrogen transfer activity of Geng Gao.Above-mentioned character has determined the Cracking catalyst provided by the invention that contains this zeolite compositions to have better cracking performance.

Example 16-18

Following example illustrates Catalysts and its preparation method provided by the invention.

(solid content is 25 weight % with zeolite compositions Z1 of the present invention and Z2 and aluminium colloidal sol respectively, the Zhou village catalyst plant is produced) or aluminium colloidal sol and kaolin (solid content is 75 weight %, Suzhou kaolin company produces) and deionized water mixing making beating, be prepared into the slurries that solid content is 25 weight %, spray-drying under 200 ℃ temperature obtains catalyst C1-C3 provided by the invention.The kind of zeolite compositions and consumption, aluminium colloidal sol, kaolinic consumption are listed in the table 8.The composition of C1-C3 is listed in the table 9.Catalyst is formed by calculating.

Comparative Examples 9-11

Following Comparative Examples explanation contains Cracking catalyst of HY zeolite and reference zeolite compositions and preparation method thereof.

Method by example 18 prepares catalyst, different is to use HY zeolite, reference zeolite compositions ZB1 and the ZB2 of (1) preparation in the example 1 to replace zeolite compositions Z2 of the present invention respectively, obtains containing reference catalyst CB1, CB2 and the CB3 of HY zeolite, reference zeolite compositions ZB1 or ZB2.Each material consumption is listed in the table 8.The composition of reference catalyst CB1-CB3 is listed in the table 9.

Example 19-23

This example illustrates Catalysts and its preparation method provided by the invention.

(solid content is 35 weight % with boehmite, the Zhou village catalyst plant is produced) mix with deionized water, be prepared into the slurries that solid content is 30 weight %, adding concentration is the aqueous hydrochloric acid solution of 36.5 volume %, regulates the pH value to 2.0 of slurries, adds zeolite compositions Z3-Z7 respectively, add aluminium colloidal sol (with example 16) and kaolin (with example 17) again, be prepared into the slurries that solid content is 20 weight %, spray-drying under 200 ℃ temperature obtains catalyst C4-C8 provided by the invention.The kind of boehmite consumption, zeolite compositions and consumption, aluminium colloidal sol consumption and kaolinic consumption are listed in the table 8, and the composition of catalyst C4-C8 is listed in the table 9.

Table 8

Example number	Each material consumption, kilogram				The combination of zeolites species
						Boehmite	Aluminium colloidal sol	Kaolin	Zeolite compositions
	16	-	12.0	-						3.0	Z1
17					-	12.0	6.0	3.0	Z1
	18	-	12.0	6.0						3.0	Z2
Contrast medium 9						12.0	6.0	3.0	HY
	Contrast medium 10		12.0	6.0						3.0	ZB1
Contrast medium 11						12.0	6.0	3.0	ZB2
	19	4.0	3.96	2.25						1.75	Z3
20					1.0	2.6	2.7	2.0	Z4
	21	2.0	1.2	2.7						2.0	Z5
22					2.9	6.0	7.3	2.0	Z6
	23	0.7	1.0	4.0						1.5	Z7

Table 9

Example number	The catalyst numbering	The combination of zeolites species	Zeolite compositions content, weight %	Alumina content, weight %	Kaolin content, weight %
						16	C1	Z1	50	50	-
17	C2	Z1	28.6	28.6	42.8
						18	C3	Z2	28.6	28.6	42.8
Contrast medium 9	CB1	HY	28.6	28.6	42.8
						Contrast medium 10	CB2	ZB1	28.6	28.6	42.8
Contrast medium 11	CB3	ZB2	28.6	28.6	42.8
						19	C4	Z3	30	41	29
20	C5	Z4	40	20	40
						21	C6	Z5	40	20	40
22	C7	Z6	20	25	55
						23	C8	Z7	30	10	60

Example 24-25

This example illustrates Catalysts and its preparation method provided by the invention.

Intending thin water aluminium (with example 19) with 3 kilograms respectively mixes with 30 kilograms of deionized waters, adding concentration is the aqueous hydrochloric acid solution of 36.5 volumes, regulate the pH value to 2.0 of slurries, adding 2.5 kilograms of zeolite compositions Z1 and Z5 respectively stirs, (silica alumina ratio is 100 to add 0.25 kilogram of ZSM-5 zeolite more respectively, sodium oxide content is 0.1 weight %, the Zhou village catalyst plant is produced) and 2.5 kilograms of REHY zeolites (specification sees Table 1), 4.8 kilogram and 5.8 kilograms of aluminium colloidal sols (with example 16) and 10 kilograms and 6.7 kilograms of kaolin (with example 17), stir, obtain the slurries that solid content is 29.4 weight %, 200 ℃ of following spray-dryings, must contain Cracking catalyst C9 provided by the invention and C10.The composition of C9 and C10 is listed in the table 10.

Table 10

Example number	24	25
			The catalyst numbering	C9	C10
The combination of zeolites species	Z1	Z5
			Zeolite compositions content, weight %	20	20
Alumina content, weight %	18	20
			Kaolin content, weight %	60	40
The REHY zeolite content, weight %	-	20
			The ZSM-5 zeolite content, weight %	2	-

Example 26-35

Following example illustrates the catalytic performance of catalyst provided by the invention.

The catalyst C1-C10 of example 16-25 preparation at 800C, was worn out 4 hours with 100% steam.On small fixed flowing bed-tion reacting device, with the decompressed wax oil shown in the catalyst cracking table 11 after above-mentioned the wearing out, catalyst loading amount 90 grams, the catalyst granules diameter is the 0.18-0.25 millimeter.Reaction condition and reaction result are respectively among the table 12-13.

Comparative Examples 12-14

Following Comparative Examples explanation contains the catalytic performance of the Cracking catalyst of HY zeolite or reference zeolite compositions.

Press the method aging catalyst of example 28 and to same feedstock oil, carry out catalytic cracking under similarity condition, different is to replace catalyst C3 with reference catalyst CB1, CB2 and CB3 respectively.Reaction condition and reaction result are listed in the table 12.

Table 11

The feedstock oil title	Decompressed wax oil
		Proportion (d 4 10), gram per centimeter 3	0.8652
Viscosity, millimeter 250 ℃ 100 ℃ of/seconds	14.58 4.37
		Carbon residue content; The % by weight boiling range, ℃ initial boiling point 10% 30% 50% 70% 90% is done	0.04 227 289 347 389 417 446 475

Table 12

Example number	26	27	28	Comparative Examples 12	Comparative Examples 13	Comparative Examples 14
							Catalyst	C1	C2	C3	CB1	CB2	CB3
Reaction temperature, ℃	500	520	482	482	482	482
							Weight space velocity, hour -1	20	16	16	16	16	16
Agent weight of oil ratio	6	8	4	4	4	4
							Conversion ratio, weight %	82	85	79	70	73	74
Product yield, weight %
							Dry gas	2.6	3.3	2.1	1.6	1.8	1.8
Liquefied gas	21.4	22.5	20.8	18.9	19.2	19.7
							Gasoline	50.2	51.2	48.9	44.5	45.1	45.5
Diesel oil	11.6	9.1	11.3	16.8	14.4	13
							Heavy oil	6.4	5.9	9.7	13.2	12.6	13
Coke	7.8	8.0	7.2	6.6	6.9	7.0
							RON	90.7	91.2	90.3	87.8	88.5	88.6

Table 13

Example number	29	30	31	32	33	34	35
								Catalyst	C4	C5	C6	C7	C8	C9	C10
Reaction temperature, ℃	492	482	510	482	482	482	482
								Weight (hourly) space velocity (WHSV), hour -1	12	16	20	16	16	16	16
Agent weight of oil ratio	3	4	6	4	4	4	4
								Conversion ratio, weight %	78	81	84	76	76.5	79.7	84.3
Product yield, weight % dry gas	2.1	2.5	3.0	2.0	2.0	2.2	3.2
								Liquefied gas	21.1	21.9	22.8	20.3	20.6	21	22.6
Gasoline	47.7	49	50.4	46.7	46.8	49.5	50.6
								Diesel oil	11.7	9.6	9.5	11.8	11.1	11.2	9.7
Heavy oil	10.3	9.4	6.5	12.2	12.4	9.1	6.0
								Coke	7.1	7.6	7.8	7.0	7.1	7.0	7.9
RON	89.4	90.7	90.9	89.1	89.2	89.6	91.0

From the result of table 12 as can be seen, adopt catalyst C3 provided by the invention, conversion ratio is up to 79 weight %, and Study of Gasoline method octane number RON is up to 90.3.And adopt to form identically, and described zeolite compositions is respectively the HY zeolite, and during the reference catalyst of ZB1 and ZB2, conversion ratio has only 70 weight % respectively, 73 weight % and 74 weight %, Study of Gasoline method octane number RON has only 87.8,88.5 and 88.6 respectively.This illustrates that catalyst provided by the invention has higher cracking activity, and the octane number of the gasoline product that obtains with Cracking catalyst cracking hydrocarbon ils provided by the invention is higher.

Example 36-38

Following example illustrates the catalytic performance of catalyst provided by the invention.

Carry out catalytic cracking by the method aging catalyst of example 26 and to feedstock oil, different is that raw materials used oil is the reduced crude shown in the table 14, and catalyst and/or reaction condition are also different, and catalyst system therefor, reaction condition and reaction result are listed in the table 15.

Table 14

The feedstock oil title	Reduced crude
		Proportion (d 4 10), gram per centimeter 3	0.8906
Viscosity, millimeter 280 ℃ of/seconds	44.18
		100℃	24.84
Carbon residue content, weight %	4.3
		Boiling range, ℃ initial boiling point	282
10％	370
		30％	482
50％	553

Table 15

Example number	36	37	38
				Catalyst	C2	C3	C5
Reaction temperature, ℃	500	500	500
				Weight space velocity, hour -1	10	10	10
Agent weight of oil ratio	5	5	5
				Conversion ratio, weight %	75.2	76.1	76.8
Product yield, weight %
				Dry gas	2.1	2.2	2.3
Liquefied gas	17.1	16.6	16.8
				Gasoline	48.7	49.9	50.2
Diesel oil	17.3	17.0	16.5
				Heavy oil	7.5	6.9	6.7
Coke	7.3	7.4	7.5
				RON	88.3	89.0	89.5

Claims (21)

1. hydrocarbon cracking catalyzer, this catalyst contains a kind of zeolite compositions and a kind of host material, base is characterised in that, described zeolite compositions contains zeolite, fluorine, silicon components and phosphorus, with the zeolite compositions is benchmark, and the content of zeolite is 50-99.5 weight %, in element fluorine, the content of fluorine is 0.1-10 weight %, with SiO ₂Meter, the content of silicon components is 0.1-20 weight %, with P ₂O ₅Meter, the content of phosphorus is 0.1-20 weight %.

2. catalyst according to claim 1 is characterized in that, the content of described zeolite is 70-99 weight %, and the content of fluorine is 0.1-5 weight %, and the content of silicon components is 0.2-10 weight %, and the content of phosphorus is 0.2-15 weight %.

3. catalyst according to claim 1 and 2 is characterized in that described zeolite is selected from one or more in large pore zeolite and the mesopore zeolite.

4. catalyst according to claim 3, it is characterized in that, described zeolite is selected from y-type zeolite, contains the y-type zeolite of rare earth, overstable gamma zeolite, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the modenite one or more.

5. catalyst according to claim 1 is characterized in that, is benchmark with the catalyst total amount, and the content of described zeolite compositions is 1-99 weight %, and the content of host material is 1-99 weight %.

6. catalyst according to claim 5 is characterized in that, the content of described zeolite compositions is 10-70 weight %, and the content of host material is 30-90 weight %.

7. catalyst according to claim 6 is characterized in that, the content of described zeolite compositions is 10-60 weight %, and the content of host material is 40-90 weight %.

8. according to claim 1,5,6 or 7 described catalyst, it is characterized in that described host material is selected from one or more in heat-resistant inorganic oxide and the clay.

9. catalyst according to claim 8, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica and the amorphous aluminum silicide, and described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.

10. catalyst according to claim 5, it is characterized in that, this catalyst contains described zeolite compositions, host material aluminium oxide, contains or does not contain the host material clay, with the catalyst total amount is benchmark, the content of described zeolite compositions is 10-70 weight %, the content of aluminium oxide is 5-60 weight %, and the content of clay is 0-75 weight %.

11. catalyst according to claim 10 is characterized in that, the content of described zeolite compositions is 10-60 weight %, and the content of aluminium oxide is 10-50 weight %, and the content of clay is 10-60 weight %.

12., it is characterized in that described clay is a kaolin according to claim 10 or 11 described catalyst.

13., it is characterized in that the zeolite in the described zeolite compositions is selected from one or more in macropore and the mesopore zeolite according to claim 10 or 11 described catalyst.

14. catalyst according to claim 13, it is characterized in that, the zeolite in the described zeolite compositions is selected from y-type zeolite, contains the y-type zeolite of rare earth, overstable gamma zeolite, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the modenite one or more.

15. according to claim 1,5 or 10 described catalyst, it is characterized in that this catalyst also contains a kind of independent component zeolite, this independent component zeolite is selected from one or more in macropore and the mesopore zeolite, with the catalyst total amount is benchmark, and the content of this independent component zeolite is 2-40 weight %.

16. catalyst according to claim 15 is characterized in that, the content of this independent component zeolite is 2-30 weight %.

17. catalyst according to claim 15, it is characterized in that, this independent component zeolite is selected from y-type zeolite, contains y-type zeolite, the overstable gamma zeolite of rare earth, the ultrastable that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the modenite one or more.

18. catalyst according to claim 17 is characterized in that, this independent component zeolite is selected from the zeolite with MFI structure and/or contains the zeolite with MFI structure of rare earth

19. claim 1 Preparation of catalysts method, this method comprises mixes making beating with zeolite compositions with the precursor and the deionized water of host material and/or host material, dry, it is characterized in that described zeolite compositions contains zeolite, fluorine, silicon components and phosphorus, is benchmark with the total amount of zeolite compositions, the content of zeolite is 50-99.5 weight %, in element, the content of fluorine is 0.1-10 weight %, with SiO ₂Meter, the content of silicon components is 0.1-20 weight %, with P ₂O ₅Meter, the content of phosphorus is 0.1-20 weight %; The preparation method of described zeolite compositions comprises zeolite is mixed jointly or step by step with the fluorine compounds aqueous solution, phosphorous compound aqueous solution and silicon compound, or with the fluorine compounds aqueous solution, phosphorous compound aqueous solution, the silicon compound aqueous solution common or step impregnation zeolite, the each mixing or dipping back drying, roasting or not roasting, the last mixing or dipping back roasting, described baking temperature is a room temperature to 300 ℃, and sintering temperature is greater than 300 ℃ to 700 ℃, and the time of roasting is more than 0.5 hour.

20. method according to claim 19, it is characterized in that, elder generation is with zeolite and silicon compound aqueous solution or flood zeolite with silicon compound earlier, dry, roasting or not roasting, with zeolite and phosphorous compound aqueous solution while or step impregnation zeolite, mix or dipping back drying, roasting or not roasting the dry also roasting of mixing for the last time or dipping back more at every turn.

21. method according to claim 19, it is characterized in that, when the precursor of described zeolite compositions and host material and/or host material is pulled an oar, also add a kind of independent component zeolite, this independent component zeolite is selected from one or more in macropore and the mesopore zeolite.