CN1272406C - Highly productive lower carbon olefin catalyst - Google Patents

Abstract

The present invention relates to a petroleum hydrocarbon cracking catalyst for increasing the yield of low-carbon olefins, which is prepared from 0 to 70% of clay, 5 to 90% of inorganic oxide and 10 to 35% of zeolite which are measured by using the catalyst weight as the reference, wherein the zeolite is a zeolite mixture prepared from 5 to 50 wt% of zeolite in an MFI structure, 10 to 35 wt% of zeolite in an MTT structure, 20 to 75 wt% of high-silicon Y-type zeolite and 1 to 25 wt% of rare earth containing Y-type zeolite. When used for catalytic cracking, the catalyst has the characteristics of high heavy oil conversion rate and high yield of the low-carbon olefins, particularly C2<=> and C3<=>.

Description

A kind of catalyzer of low-carbon olefines high-output

Technical field

The invention relates to a kind of catalyzer that low-carbon alkene is produced in the petroleum hydrocarbon cracking that is used for.More particularly, the invention relates to a kind of catalyzer that contains crystal silicon-aluminate zeolite that low-carbon alkenes such as ethene, propylene are produced in the petroleum hydrocarbon cracking that is used for.

Technical background

Produce low-carbon alkenes such as ethene, propylene from petroleum hydrocarbon, generally the method for Cai Yonging is to be the pyrolysis in tubular furnace of raw material with Sweet natural gas, petroleum naphtha or solar oil, or is the heat carrier cracking of raw material with the heavy hydrocarbon.But conventional catalytic cracking unit also by-product low-carbon alkene when producing gasoline and diesel oil, but its output only accounts for below the 15 heavy % of stock oil.

Kai Fa catalytic pyrolysis is to be the technology of raw material production low-carbon alkene with the heavy petroleum hydrocarbon in recent years, and the catalyzer relevant with it also has a lot of bibliographical informations.

The composite molecular sieve catalyst that the catalyzer that discloses among the CN1117518A is made up of five-membered ring structure high-silicon zeolite that contains phosphorus and rare earth and y-type zeolite etc.

Disclose a kind of catalyzer that is used for catalytic thermal cracking process to prepare lower olefine among the CN1222558A, wherein also contained the supersiliceous zeolite and the y-type zeolite of five-membered ring structure.

CN1354224A has developed a kind of catalyzer of producing propylene, and wherein used zeolite is the mixture of y-type zeolite and β zeolite or mordenite or ZRP zeolite.

CN1230148A has developed the method that a kind of usefulness contains the alkene production catalyst of five-membered ring structure zeolite, and the silica alumina ratio of its mesolite is 20-800.

CN1114916A discloses a kind of catalyzer that is used for the petroleum hydrocarbon preparing low-carbon olefin by conversion, it is made up of the clay of 0-70 weight %, the inorganic oxide of 5-90 weight % and the zeolite of 10-35 weight %, and its mesolite is made up of the five-ring supersiliceous zeolite of the phosphorous and rare earth of 20-75 weight %, the type-Y high silicon zeolite of 20-75 weight % and the y-type zeolite that contains rare earth of 1-25 weight %.That this catalyzer has in the product is third rare, the high characteristics of productive rate of iso-butylene and isopentene.

Summary of the invention

The objective of the invention is to provide on the basis of existing technology another kind of catalytic cracking catalyst, in the hope of the productive rate of higher low-carbon alkene, particularly ethene and propylene in the acquisition product.

Petroleum hydrocarbon catalyst for cracking provided by the invention is clay, the inorganic oxide of 5-90% and the zeolite of 10-35% that benchmark has following composition: 0-70% with the catalyst weight, the zeolite mixture that said zeolite is made up of the y-type zeolite that contains rare earth of the type-Y high silicon zeolite of the zeolite with MTT structure of the zeolite with MFI structure of the heavy % of 5-50, the heavy % of 10-35, the heavy % of 20-75 and the heavy % of 1-25.

The wherein said MFI of having structural zeolite is that a kind of aperture is ten-ring, has a Si-Al zeolite of three-dimensional open-framework, it has the double hole channel size of 5.1 * 5.5 and 5.3 * 5.6 , its most typical representative is the zeolite of ZSM-5 class, for example ZSM-5, NU-5, ZRP (trade(brand)name) etc.Silicon oxide with MFI structural zeolite and alumina molar ratio used among the present invention are advisable with 30-300, preferred 50-100.

The wherein said MTT of having structural zeolite is that a kind of aperture is a ten-ring, Si-Al zeolite with one-dimensional tunnel structure, and its duct size is 4.5 * 5.2 , and it has X-ray diffraction spectrogram as shown in Figure 1, its most typical representative such as ZSM-23, EU-13 etc.Silicon oxide with MTT structural zeolite and alumina molar ratio used among the present invention are advisable with 15-150, preferred 50-100.

Wherein said type-Y high silicon zeolite is with chemistry and/or physical method, as hydrothermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method, SiCl ₄That obtain, that contain or do not contain rare earth after method is handled, stabilization y-type zeolite.

The wherein said y-type zeolite that contains rare earth is selected from Rare Earth Y (REY), rare earth hydrogen Y (REHY) and composition thereof.

Catalyst for cracking of the present invention has no particular limits the carrier that is adopted, and the common employed carrier of cracking catalyst gets final product in the use prior art.The what is called " semi-synthetic carrier " that wherein preferably contains clay and inorganic oxide binder.Wherein said clay is kaolin or halloysite preferably; Said inorganic oxide is silicon oxide, aluminum oxide and composition thereof preferably, wherein preferably pseudo-boehmite or aluminium colloidal sol or its mixture of the precursor of aluminum oxide.

Catalyst for cracking of the present invention has no particular limits its preparation method, and the common employed preparation method of cracking catalyst gets final product in the use prior art.

Catalyzer provided by the invention has heavy oil conversion rate height and low-carbon alkene, especially C when being used for catalytic pyrolysis ₂ ⁼And C ₃ ⁼The characteristics that productive rate is high.

Description of drawings

Fig. 1 is the X-ray diffraction spectrogram with MTT structural zeolite.

Embodiment

The following examples will illustrate further to the present invention, but not thereby limiting the invention.

The place of production of used various raw materials and specification are as follows in embodiment and the Comparative Examples:

Kaolin: hard paste porcelain God in charge of the Earth Sigong industry product, solid content are 80 heavy %.

Pseudo-boehmite: Shandong Aluminum Plant's Industrial products, Al ₂O ₃Content is 95 heavy %, and solid content is 30%.

Aluminium colloidal sol: Shandong, Shandong catalyst plant Industrial products, Al ₂O ₃Content is 11.4 heavy %.

The MFI structural zeolite: Shandong, Shandong catalyst plant Industrial products, trade(brand)name ZRP, silica alumina ratio are 60.

The MTT structural zeolite is according to document (S.Ernst, R.Kumar, J.Weitkamp, in ZeoliteSynthesis, Am.Chem.Soc.Symposium Series 398, M.Occell i, H.Robson (eds.), 1989, pp 560-573) synthetic method that provides in is prepared into.The zeolite that will synthesize roasting 3 hours under 550 ℃ of air atmospheres exchanges to sodium content (with Na with ammonium nitrate ₂The O meter) is lower than 0.1 weight %,, promptly obtains preparing the used MTT zeolite of catalyzer again 500 ℃ of following roastings 2 hours.

Hyperastable Y-type RE (REUSY) type zeolite: Shandong, Shandong catalyst plant Industrial products, with RE ₂O ₃The heavy % in the content of rare earth of meter＜3.0.

REY type zeolite: Shandong, Shandong catalyst plant Industrial products, SiO ₂/ Al ₂O ₃＞4.7, with RE ₂O ₃The heavy % in the content of rare earth of meter＞17.

REHY type zeolite: Shandong, Shandong catalyst plant Industrial products, with RE ₂O ₃The heavy % in the content of rare earth of meter＜7.

Comparative Examples

The prior art Preparation of catalysts of the no MTT structural zeolite of this Comparative Examples explanation.

With 340 kilograms of decationizing water 160 kilograms of halloysites are pulled an oar, add 150 kilograms of pseudo-boehmites again, transfer pH=2-4 with hydrochloric acid, stir, wore out 1 hour down at 75 ℃, cool the temperature to below 60 ℃, add zeolite mixture and 70 kilograms of decationizing water of MFI structural zeolite, REY and REUSY, stir spray drying forming, the flush away free sodium is drying to obtain the comparative catalyst.The catalyzer composition sees Table 1.

Embodiment 1-3

These examples illustrate Preparation of catalysts provided by the invention.

With 340 kilograms of decationizing water 160 kilograms of halloysites are pulled an oar, add 150 kilograms of pseudo-boehmites again, transfer pH=2-4 with hydrochloric acid, stir, wore out 1 hour down at 75 ℃, cool the temperature to below 60 ℃, add zeolite mixture and 70 kilograms of decationizing water of MFI structural zeolite, MTT structural zeolite, REHY, REY and REUSY, stir spray drying forming, the flush away free sodium is drying to obtain catalyst sample A, B and C.

Each Preparation of Catalyst materials amount and sample sets become to see Table 1.

Table 1

Catalyzer	Contrast medium	A	B	C
					Halloysite, kilogram	160	160	160	160
Pseudo-boehmite, kilogram	150	150	150	150
					The mixed zeolite amount, kilogram	51	51	51	51
Catalyzer is formed, heavy %
					Kaolin	59.0	59.0	59.0	56.0
Aluminum oxide	19.0	19.0	19.0	18.0
					Zeolite	22.0	22.0	22.0	26.0
MFI	45.5	38.0	28.0	21.0
					MTT	0	8.0	18.0	25.0
REY	9.1	9.0	0	4.5
					REHY	0	0	9.0	4.5
REUSY	45.4	45.0	45.0	45.0

Embodiment 4-6

These example explanations the invention provides the catalytic performance of catalyzer.

Prepared sample among above-mentioned Comparative Examples and the embodiment is carried out the evaluation of catalytic performance respectively on small fixed flowing bed.Before estimating, handled 6 hours through normal pressure, 800 ℃, 100% steam aging in advance catalyst sample.The catalyst sample loading amount is 180 grams during evaluation, and the evaluation response temperature is 520 ℃, and weight space velocity is 1 hour ^-1, agent-oil ratio is 5.Estimating raw materials used oil is the paraffinic base wax oil, and its character sees Table 2.The evaluation result of each catalyst sample sees Table 3.

By table 3 data as can be seen, catalyzer provided by the invention is compared its low-carbon alkene, especially C with contrast medium when keeping higher heavy oil conversion ₂ ⁼And C ₃ ⁼Yield higher.

Table 2

Density (20 ℃) g/cm3	The heavy % of electric furnace process carbon residue	Alkali nitrogen ppm	Boiling range ℃
				0.8560	0.70	420	319-503

Table 3

Catalyzer	Contrast medium	A	B	C
					Transformation efficiency, heavy % product distributes, heavy % reacted gas gasoline, diesel heavy oil coke is olefins yield wherein, heavy % C 2 ＝ C 3 ＝ C 2 ＝-C 5 ＝	81.87 38.11 38.75 10.77 7.36 5.01 1.46 14.12 32.33	81.21 38.13 38.10 11.21 7.58 4.98 1.53 15.23 34.12	80.53 37.89 37.78 11.82 7.65 4.86 1.51 15.25 34.23	81.06 38.21 37.84 11.65 7.29 5.01 1.62 15.42 34.52

Claims (6)

1, a kind of petroleum hydrocarbon catalyst for cracking of low-carbon olefines high-output, with the catalyst weight is that benchmark has following composition: the clay greater than zero and no more than 70%, 5-90% is selected from silicon oxide, inorganic oxide of aluminum oxide and composition thereof and the zeolite of 10-35%, it is characterized in that wherein said zeolite is the zeolite with MFI structure by the heavy % of 5-50, the zeolite of the heavy % of 10-35 with MTT structure, the zeolite mixture that the y-type zeolite that contains rare earth of the type-Y high silicon zeolite of the heavy % of 20-75 and the heavy % of 1-25 is formed, the silicon oxide of the said MFI of having structural zeolite and alumina molar ratio are 30-300, and the silicon oxide of the said MTT of having structural zeolite and alumina molar ratio are 15-150.

2,, it is characterized in that the silicon oxide of the said MFI of having structural zeolite and alumina molar ratio are 50-100 according to the described catalyzer of claim 1.

3,, it is characterized in that the silicon oxide of the said MTT of having structural zeolite and alumina molar ratio are 50-100 according to the described catalyzer of claim 1.

4, according to the described catalyzer of claim 1, it is characterized in that said type-Y high silicon zeolite be obtain after handling with chemistry and/or physical method contain or do not contain rare earth and stabilization y-type zeolite.

5,, it is characterized in that the said y-type zeolite that contains rare earth is selected from Rare Earth Y, rare earth hydrogen Y and composition thereof according to the described catalyzer of claim 1.

6,, it is characterized in that said clay is selected from kaolin or halloysite according to the described catalyzer of claim 1.