CN1485408A - Method for preparing cracking catalyst - Google Patents

Abstract

A method of preparing cracking catalysts. It comprises : mixing NaY molecular sieve with an ammonium salt-water composition containing 20-90% ammonium salt by weight at 90degree C-160degree C, and making them contact for 10min-10hours, Na2O in the molecular sieve is lowered down to below 2% by weight, mixing with a carrier, then getting the catalyst. The method could shorten the process, and reduce energy consumption.

Description

A kind of preparation method of cracking catalyst

Technical field

The invention relates to a kind of preparation method of cracking catalyst, the preparation method who further says so and contain the cracking catalyst of Y zeolite about a kind of.

Background technology

The step of prior art for preparing cracking catalyst is: (1) NaY molecular sieve after filtration, the exchange of ammonium, dry, step such as water roasting, the exchange of secondary ammonium, drying and the roasting of secondary water make ultra-steady Y molecular sieve; (2) ultra-steady Y molecular sieve mixes with carrier through making beating, after grinding, and spray-dried again, washing and drying and other steps obtain product.For example, disclosed method is to adopt 3%～5% ammonium salt solution repeatedly to exchange the sodium content that reduces in the molecular sieve among the USP4415439, adopt once or twice that roasting prepares super stable molecular sieve, become glue to spray drying one-tenth catalyzer through grinding the making beating back with carrier super steady Y again.

As can be seen, the existing cracking catalyst that contains super-stable Y molecular sieves exists that long flow path, energy consumption are big, loss is many, molecular sieve disadvantage such as poor dispersion in carrier in preparation.

Summary of the invention

Purpose of the present invention is exactly at the deficiencies in the prior art, and the preparation method of the cracking catalyst that a kind of flow process is short, energy consumption is low is provided.

The preparation method of cracking catalyst provided by the invention is characterized in that NaY molecular sieve and the ammonium salt-water mixture that contains 20～90 heavy %, preferred 30～80 heavy % ammonium salts are contacted mixing 10 minutes～10 hours under 90 ℃～160 ℃, makes Na in the molecular sieve ₂O content mixes with carrier after being reduced to below the 2 heavy %, and the preparation process through routine obtains again.

In the method provided by the invention, said ammonium salt is selected from (NH ₄) ₂SO ₄, NH ₄NO ₃Or NH ₄A kind of among the Cl or two or more mixture in them.

In the method provided by the invention, said cracking catalyst is formed the clay of binding agent that wherein said carrier is 10～80 heavy % and 20～90 heavy % by Y zeolite and 60～90 heavy % carriers of 10～40 heavy %.

Said binding agent can be selected from a kind of in aluminium colloidal sol, pseudo-boehmite, silicon sol, the phosphorus aluminium glue or two or more mixture wherein, the double aluminium binder that wherein preferred aluminium colloidal sol and pseudo-boehmite are formed.

Said clay is the cracking catalyst common clay, as kaolin, the intercalation soil of Peng, sepiolite etc.

In the method provided by the invention, its degree of crystallinity of said NaY greater than 80%, SiO ₂/ Al ₂O ₃Be 3～6, Na ₂O content is 8～12%; Said NaY also can be through the NaY after the conventional exchange, its Na ₂O content is lower than 4.5 heavy %, and said conventional exchange is meant with 2%～5% ammonium salt aqueous solution 70 ℃～90 ℃ processes that contact with molecular sieve down.

In the method provided by the invention, said conventional preparation process comprises processes such as filtration, drying, roasting, washing.

Adopt the preparation method of cracking catalyst provided by the invention, have the following advantages:

(1) method provided by the invention, can drop to below the 2 heavy % by a sodium content that go on foot molecular sieve, filter cake directly mixes with carrier, molecular sieve is not assembled, dispersity is better, has overcome the long flow path that exists in the conventional preparation Y molecular sieve cracking catalysis agent method, energy consumption is big, loss is many, the deficiency of molecular sieve poor dispersion in carrier.

(2) cracking catalyst of employing method preparation provided by the invention has higher light oil microactivity than the catalyzer of prior art for preparing.For example, the catalyzer of the preparation of method described in the example, light oil microactivity are 75 all more than 77 and adopt the light oil microactivity of the catalyzer of prior art for preparing in the Comparative Examples.

Embodiment

Following example will the invention will be further described.

Reagent used in the example is except that special mark, and its specification is chemical pure.

Example 1

With (NH ₄) ₂SO ₄, water and NaY according to 10: 10: 1 weight ratio with (NH ₄) ₂SO ₄Mix with water stir after, add NaY molecular sieve (its Na ₂O content is 3.5%, and degree of crystallinity is 85.9, and structure cell is 24.71), be warming up to 106 ℃, constant temperature stirred 1 hour, and filtration washing is to there not being SO ₄ ^2-, its Na ₂O content is 1.1 heavy %.

350 grams (solid content 70%) through above-mentioned steps handle the molecular sieve filter cake, (contain Al with 200 gram pseudo-boehmites (solid content 34.8 heavy %, Shandong Aluminum Plant's product), 100 gram aluminium colloidal sols ₂O ₃21 heavy %, Qilu Petrochemical company catalyst plant product) and 350 gram kaolin (solid content 85.0%, China Kaolin Co., Ltd's Industrial products) mix and stirred 30 minutes, filter back 120 ℃ of dryings, 550 ℃ of roastings, again through wash and drying after make catalyzer.

This catalyzer molecular sieve lattice constant behind 800 ℃ of 4 hours hydrothermal agings is 24.34 , and light oil microactivity is 80%.

Example 2～15

When method provided by the invention is adopted in example 2～15 explanation, molecular sieve, the ammonium sulfate influence different with the ratio of water consumption.The Na of raw material molecular sieve in the example 2～5 wherein ₂O content is 3.5 heavy %, the Na of raw material molecular sieve in the example 6～15 ₂O content is 8.9 heavy %.

Other raw material and preparation process are with example 1.

Table 1

Example number	(NH 4) 2SO 4∶H 2O∶NaY	Na in the filter cake 2O content (heavy %)	The lattice constant () of catalyzer molecular sieve behind 800 ℃ of 4 hours hydrothermal agings	Light oil microactivity (%)
					?2	????2∶3∶1	????1.9	????24.33	????85
?3	????3∶3∶1	????1.8	????24.32	????86
					?4	????6∶6∶1	????1.6	????24.32	????88
?5	????10∶10∶1	????1.1	????24.32	????89
					?6	????11∶10∶1	????1.9	????24.33	????86
?7	????8∶10∶1	????2.2	????24.33	????84
					?8	????7∶10∶1	????2.2	????24.32	????84
?9	????6∶10∶1	????2.3	????24.35	????83
					?10	????5∶10∶1	????2.3	????24.36	????83
?11	????4∶10∶1	????2.5	????24.35	????81
					?12	????3∶10∶1	????2.7	????24.38	????81
?13	????8.8∶9∶1	????2.4	????24.36	????82
					?14	????5.5∶6∶1	????2.7	????24.36	????80
?15	????3.3∶3∶1	????3.1	????24.34	????77

From the result of table 1 as can be seen, (NH ₄) ₂SO ₄Consumption is big more, the residual Na of molecular sieve ₂O content is low more; Water consumption is big more, the residual Na of molecular sieve ₂O content is low more.Catalyzer through the lattice constant of molecular sieve behind 800 ℃ of 4 hours hydrothermal agings all between 24.30 ～24.39 .

Example 16～28

NaY molecular sieve, the influence different of ammonium nitrate consumption when the explanation of this example is handled with the ammonium nitrate-water mixture of different ammonium amounts with the ratio of water consumption.

The raw molecule sieve is with example 6.

Table 2

Example number	NH 4NO 3∶H 2O∶NaY	Na in the filter cake 2O content (heavy %)	The lattice constant () of catalyzer molecular sieve behind 800 ℃ of 4 hours hydrothermal agings	Light oil microactivity (%)
					??16	????22∶6∶1	????0.74	????24.33	????89
??17	????24∶3∶1	????0.91	????24.32	????89
					??18	????17∶3∶1	????1.4	????24.32	????87
??19	????13∶3∶1	????1.4	????24.32	????87
					??20	????9∶3∶1	????2.0	????24.33	????85
??21	????5∶3∶1	????2.5	????24.33	????82
					??22	????6∶1∶1	????2.3	????24.32	????83
??23	????12∶2∶1	????1.5	????24.35	????86
					??24	????4∶1∶1	????2.5	????24.36	????82
??25	????8∶2∶1	????1.7	????24.35	????87
					??26	????18∶6∶1	????1.9	????24.38	????85
??27	????15∶6∶1	????1.2	????24.36	????88
					??28	????12∶6∶1	????1.7	????24.36	????86

By table 2 result as can be seen, adopt NH ₄NO ₃The time the sodium effect of falling be better than (NH ₄) ₂SO ₄, NH ₄NO ₃Consumption is big more, residual Na in the molecular sieve filter cake ₂O content is low more; Water consumption is big more, residual Na in the molecular sieve filter cake ₂O content is low more.

Example 29～32

Temperature that the explanation of this example is different and the influence of duration of contact.

Raw material and other operational conditions are distinguished as shown in table 3 with example 2.

Table 3

Example number	Treatment condition	NaO in the filter cake 2Content (heavy %)	The lattice constant () of catalyzer molecular sieve behind 800 ℃ of 4 hours hydrothermal agings	Light oil microactivity (%)
					????29	90 ℃ 1 hour	????2.5	????24.33	????81
????30	160 ℃ 1 hour	????1.6	????24.32	????87
					????31	140 ℃ 1 hour	????1.8	????24.33	????86
????32	120 ℃ 1 hour	????2.0	????24.32	????85

Comparative Examples

This Comparative Examples explanation prior art is the cracking catalyst of active ingredient with two ultra-steady Y molecular sieves of handing over two roastings to be equipped with.

150 gram super-stable Y molecular sieves (solid contents 70%, Chang Ling catalyst plant product), mixes stirring 30 minutes, filter back 120 ℃ of dryings with 200 gram pseudo-boehmites, 100 gram aluminium colloidal sols and 350 gram kaolin, 550 ℃ of roastings make catalyzer again after washing and drying.This catalyzer through 800 ℃ 4 hours aging after the Y zeolite structure cell be 24.33 , light oil microactivity is 75%.

Claims (9)

1, a kind of preparation method of cracking catalyst is characterized in that NaY molecular sieve and the ammonium salt-water mixture that contains 20～90 heavy % ammonium salts are contacted mixing 10 minutes～10 hours under 90 ℃～160 ℃, makes Na in the molecular sieve ₂O content mixes with carrier after being reduced to below the 2 heavy % again, and frequent regulation is equipped with step and obtains.

2, in accordance with the method for claim 1, ammonium salt-containing 30～80 heavy % in wherein said ammonium salt-water mixture.

3, according to claim 1 or 2 described methods, wherein said ammonium salt is selected from (NH ₄) ₂SO ₄, NH ₄NO ₃Or NH ₄A kind of among the Cl or two or more mixture in them.

4, in accordance with the method for claim 1, wherein said cracking catalyst is made up of the molecular sieve of 10～40 heavy % and the carrier of 60～90 heavy %.

5, in accordance with the method for claim 4, the clay of wherein said carrier binding agent that is 10～80 heavy % and 20～90 heavy %.

6, according to the method for claim described 5, wherein said binding agent is selected from a kind of in aluminium colloidal sol, pseudo-boehmite, silicon sol, the phosphorus aluminium glue or two or more mixture wherein.

7, in accordance with the method for claim 5, the wherein said binding agent mixture that is aluminium colloidal sol and pseudo-boehmite.

8, in accordance with the method for claim 1, wherein said NaY degree of crystallinity be greater than 80%, SiO ₂/ Al ₂O ₃Be 3～6, Na ₂O content is 8～12 heavy %.

9, in accordance with the method for claim 1, wherein said NaY molecular sieve also can descend exchange to make its Na with the ammonium salt aqueous solution of 2～5 heavy % at 70～90 ℃ earlier ₂O content is lower than 4.5 heavy %.