CN1267530C

CN1267530C - Highly productive lower carbon olefin catalyst and its preparation

Info

Publication number: CN1267530C
Application number: CN 03146472
Authority: CN
Inventors: 王殿中; 罗一斌; 舒兴田; 何鸣元
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2003-07-16
Filing date: 2003-07-16
Publication date: 2006-08-02
Anticipated expiration: 2023-07-16
Also published as: CN1570032A

Abstract

The present invention relates to a catalyst for preparing low-carbon olefins by converting petroleum hydrocarbons, which is prepared from 0 to 70 wt% of clay, 5 to 90 wt% of inorganic oxide and 10 to 35 wt% of zeolite, wherein the zeolite is a zeolite mixture of 5 to 50 wt% of zeolite in an MFI structure, 10 to 35 wt% of zinc containing and/or ferrum containing 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; the metal containing zeolite in an MTT structure is prepared by being impregnated with an impregnating liquid prepared from metallic salt, 0 to 90 wt% of ethanol and 10 to 100 wt% of water. The catalyst has the characteristic that the yield of the low-carbon olefins in products, particularly the yield of ethene and the yield of propene are high.

Description

A kind of catalyzer of low-carbon olefines high-output and preparation thereof

Technical field

The invention relates to a kind of Catalysts and its preparation method that low-carbon alkene is produced in the petroleum hydrocarbon cracking that is used for.More particularly, the invention relates to a kind of Catalysts and its preparation method 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.Another source of low-carbon alkene then is the by product that conventional catalytic cracking is produced 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.

Disclosed a kind of catalyzer among the CN1114916A, by the composite zeolite catalyst that five-ring supersiliceous zeolite and y-type zeolite etc. are formed, five-ring supersiliceous zeolite wherein contains phosphorus and rare earth.

CN1222558A has disclosed a kind of catalyzer that is used for catalytic thermal cracking process to prepare lower olefine, and zeolite wherein is the composite zeolite of five-ring supersiliceous zeolite and y-type zeolite, and this five-ring supersiliceous zeolite is element modified through phosphorus, aluminium, magnesium, calcium etc.

CN1354224A has developed the catalyzer that isoparaffin gasoline, propylene and Trimethylmethane are rich in a kind of production, and wherein used zeolite is the mixture of y-type zeolite and β zeolite or mordenite or ZRP zeolite.

USP6,222,087 disclose a kind of phosphorated ZSM-5 or ZSM-11 zeolite catalyst, and purpose is to produce low-carbon alkene.

USP6,548,725 have developed and a kind of the process of low-carbon alkene have been produced in the petroleum naphtha cracking, wherein phosphorous the and gallium of catalyst system therefor, germanium, tin.

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 split product.

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

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.Used among the present invention have a preferred ZSM-5 of MFI structural zeolite, and its silicon oxide and alumina molar ratio are advisable with 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 50-100, and this zeolite contains in zinc oxide compound, that account for MTT structural zeolite weight 0.2-5%, preferred 1-3% or/and iron.

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, use that the common employed preparation method of cracking catalyst get final product in the prior art, the precursor that is about to clay, inorganic oxide aluminium is mixed, making beating, pH be aging under the tart condition, add zeolite mixture homogeneous, spraying drying and wash.

But then, what will particularly point out among the preparation method of catalyst for cracking of the present invention is to contain zinc or/and the preparation with MTT structural zeolite of iron should be carried out according to following method: with zinc nitrate and iron nitrate respectively as zinc source and source of iron, according to the amount of on zeolite, intending load, they are dissolved in the solution of being made up of the water of the ethanol of the heavy % of 0-90 and the heavy % of 10-100 make steeping fluid, according to the equivalent impregnation method of routine zeolite is flooded dry then, roasting again in steeping fluid.

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.Occelli, 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) be lower than 0.1 heavy %, again 500 ℃ of roastings 2 hours, promptly obtain preparing the used MTT zeolite of catalyzer, its silica alumina ratio is 60.

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.

Embodiment 1-5

These embodiment illustrate the preparation of iron content MTT structural zeolite.

Certain amount of ferric nitrate and/or zinc nitrate are added in a certain amount of water or the alcohol-water, stir, add 20 kilograms of silica alumina ratios again and be 60 MTT zeolite, room temperature dipping 3 hours, roasting was promptly prepared catalyst A, B, C, the used zeolite of D, E in 3 hours respectively under 120 ℃ of dry down 5 hours, 500 ℃ air atmospheres, and it is numbered a, b, c, d, e separately.The preparation parameter of each sample sees Table 1.

Table 1

Example	Iron nitrate, kg	Zinc nitrate, kg	Water, kg	Ethanol, kg	The zeolite numbering
Example	Iron nitrate, kg	Zinc nitrate, kg	Water, kg	Ethanol, kg	The zeolite numbering	1	0.90	0	22	0	a
2	0.90	0	20	2	b	1	0.90	0	22	0	a
2	0.90	0	20	2	b	3	0.30	0.23	16	6	c
4	0.90	0.14	12	10	d	3	0.30	0.23	16	6	c
4	0.90	0.14	12	10	d	5	0.61	1.15	13	9	e

Embodiment 6-10

These embodiment illustrate the preparation of catalyst sample 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, cool the temperature to below 60 ℃ at 75 ℃, add the MFI structural zeolite, be numbered zeolite mixture and 70 kilograms of decationizing water of MTT structural zeolite, REHY, REY and the REUSY of a_e, stir spray drying forming, the flush away free sodium, be drying to obtain catalyst sample A, B, C, D, E.The catalyzer composition sees Table 2.

Table 2

Catalyzer		Contrast medium	A	B	C	D	E
Catalyzer		Contrast medium	A	B	C	D	E	MTT zeolite numbering		/	a	b	c	d	e
The MTT metal content, %	Fe ₂O ₃	/	1.5	1.5	0.5	1.5	2.0	MTT zeolite numbering		/	a	b	c	d	e
	Fe ₂O ₃	/	1.5	1.5	0.5	1.5	2.0	ZnO	/	0	0	0.5	0.3	2.5
	The pseudo-boehmite amount, kilogram mixed zeolite amount, kilogram		150 51	150 51	150 51	150 51	150 51	ZnO	/	0	0	0.5	0.3	2.5	150 51
Catalyst forms, and heavy % kaolin alumina zeolites is MFI MTT REY REHY REUSY wherein			150 51	150 51	150 51	150 51	150 51	59.0 19.0 22.0 45.5 0 9.1 0 45.4	59.0 19.0 22.0 38.0 8.0 9.0 0 45.0	59.0 19.0 22.0 38.0 8.0 9.0 0 45.0	58.0 19.0 23.0 36.0 10.0 0 9.0 45.0	56.0 18.0 26.0 28.0 18.0 7.0 2.0 45.0	60.0 19.0 21.0 15.0 30.0 4.5 4.5 46.0		150 51

Embodiment 11-15

These embodiment explanations the invention provides the catalytic pyrolysis performance of catalyzer.

Catalyst sample is estimated on small fixed flowing bed, and temperature of reaction is 520 ℃, and weight space velocity is 1 hour ^-1, agent-oil ratio is 5, the catalyzer loading amount is 180 grams.Handled 6 hours through normal pressure, 800 ℃, 100% steam aging in advance before the evaluating catalyst.Testing raw materials used oil is the paraffinic base wax oil, and its character is as shown in table 3.The evaluation result of catalyzer is as shown in table 4.For the purpose of contrast, the evaluation result of comparative example also one is listed in table 4.

By table 4 data as can be seen, use catalyzer of the present invention when keeping higher heavy oil conversion, compare its low-carbon alkene, especially C with contrast medium ₂ ⁼And C ₃ ⁼Yield higher.

Table 3

Density (20 ℃), g/cm ³	The electric furnace process carbon residue, heavy %	Alkali nitrogen ppm	Boiling range ℃
Density (20 ℃), g/cm ³	The electric furnace process carbon residue, heavy %	Alkali nitrogen ppm	Boiling range ℃	0.8560	0.70	420	319-503

Table 4

Catalyzer	Contrast medium	A	B	C	D	E
Catalyzer	Contrast medium	A	B	C	D	E	Transformation efficiency, heavy %	81.87	81.27	81.36	81.25	81.16	81.11
Product distributes, heavy % reacted gas gasoline, diesel heavy oil coke is olefins yield wherein, heavy % C ₂ ^＝ C ₃ ^＝	38.11 38.75 10.77 7.36 5.01 1.46 14.12	38.71 37.58 11.15 7.58 4.98 1.60 15.86	38.89 37.45 11.03 7.61 5.02 1.65 16.21	38.68 37.51 11.17 7.58 5.06 1.68 15.89	38.90 37.23 11.62 7.32 5.03 1.66 16.30	39.02 36.85 11.27 7.62 5.24 1.62 16.23	Transformation efficiency, heavy %	81.87	81.27	81.36	81.25	81.16	81.11
	38.11 38.75 10.77 7.36 5.01 1.46 14.12	38.71 37.58 11.15 7.58 4.98 1.60 15.86	38.89 37.45 11.03 7.61 5.02 1.65 16.21	38.68 37.51 11.17 7.58 5.06 1.68 15.89	38.90 37.23 11.62 7.32 5.03 1.66 16.30	39.02 36.85 11.27 7.62 5.24 1.62 16.23	C ₂ ^＝-C ₅ ^＝, heavy %	32.33	35.62	36.03	35.78	36.14	36.11

Claims

1, a kind of catalyzer that is used for the petroleum hydrocarbon preparing low-carbon olefin by conversion, be by greater than zero and be not more than 70% clay, 5-90% is selected from silicon oxide, inorganic oxide of aluminum oxide and composition thereof and the zeolite of 10-35% are formed, it is characterized in that said zeolite is the zeolite with MFI structure by the heavy % of 5-50, the heavy % of 10-35 contains zinc or/and the zeolite with MTT structure of iron, 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 said MTT structural zeolite and alumina molar ratio are 50-100, wherein contain in oxide compound, the zinc that accounts for MTT structural zeolite weight 0.2-5% is or/and iron.

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

3, according to the described catalyzer of claim 1, it is characterized in that said MFI structural zeolite is ZSM-5, its silicon oxide and alumina molar ratio are 50-100.

4,, it is characterized in that containing in the said MTT structural zeolite in zinc oxide compound, that account for MTT structural zeolite weight 1-3% or/and iron according to the described catalyzer of claim 1.

5,, it is characterized in that said high-silicon Y-Zeolite is the y-type zeolite of having handled containing of obtaining or not containing rare earth and stabilization with chemistry and/or physical method according to the described catalyzer of claim 1.

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

7, claim 1 Preparation of catalysts method, be by a certain percentage with clay, the precursor of inorganic oxide is mixed, making beating, at pH is aging under the tart condition, the zeolite that adds the MFI structure, contain zinc or/and the zeolite with MTT structure of iron, the zeolite mixture homogeneous of type-Y high silicon zeolite and the y-type zeolite composition that contains rare earth, spraying drying and washing obtain, it is characterized in that saidly containing zinc or/and the preparation with MTT structural zeolite of iron is carried out according to following method: with zinc nitrate and iron nitrate respectively as zinc source and source of iron, according to the amount of on zeolite, intending load, they are dissolved in the solution of being made up of the water of the ethanol of the heavy % of 0-90 and the heavy % of 10-100 make steeping fluid, according to the equivalent impregnation method of routine zeolite is flooded in steeping fluid again, dry then, roasting.