CN106925336A - A kind of Resid Fcc Catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of Resid Fcc Catalyst and preparation method thereof, step is as follows：(1) the rotation fine powder of catalytic cracking three is in oxalic acid and oleum mixed solution high temperature reaction a period of time；(2) product in step (1) is filtered and is washed with water to certain pH value；(3) filter cake in step (2) and Rare Earth Y are added into a certain amount of water, and will be adjusted to certain pH value using phosphoric acid, be designated as solution A；(4) a certain amount of kaolin, boehmite and Alumina gel are beaten mixing mashing with water, certain pH value is transferred to phosphoric acid, obtain solution B.(5) solution A and solution B cocurrent are added into quick mixing；(6) by the slurries mist projection granulating of step (5), wash, dry.Preparation method of the invention, three modified rotation fine powders have suitable gradient pores distribution and suitable acidity and acid strength, advantageously reduce slurry oil yield and improve catalyst coke selectivity；The introducing of part P elements during synthetic catalyst, further increases the number at catalyst acid center, strengthens slag oil cracking, produces more light oils；Three rotation fine powders are realized recycling in the synthesis of catalyst, reduce environmental pollution.

Description

A kind of Resid Fcc Catalyst and preparation method thereof

Technical field

The invention belongs to catalyst technical field, and in particular to a kind of Resid Fcc Catalyst and preparation method thereof, It can reduce slurry oil and improve coke selectivity.

Background technology

Catalytic cracking occupies critical role in petroleum refining industry of China, and 70% gasoline, 30% diesel oil carrys out self-catalysis and splits Change.How as far as possible by converting crude oil into light oil (gasoline+diesel oil), coke and dry gas yied, direct relation are reduced as far as possible To the economic benefit of oil plant.

Orifice diameter due to residual oil macromolecular diameter much larger than Y type molecular sieve, it is impossible to be directly entered in molecular sieve pore passage Carry out cracking, thus residual oil molecule need to be carried out on catalyst substrates it is precracked.The matrix needs suitable aperture and acid Intensity.

CN101745373A reports a kind of assistant for calalytic cracking, it is characterized in that two kinds of aluminum oxide containing gradient distribution, One kind is macroporous aluminium oxide, and one kind is small porous aluminum oxide.

CN1978593B reports a kind of catalytic cracking catalyst, it is characterized in that contain mesoporous material, the mesoporous material by Aluminum oxide, silica, magnesia or rare earth oxide composition.

CN103007981A reports a kind of Resid Fcc Catalyst, by REUSY molecular sieves, the 5-- of 15--35% 25% silicon magnesium glue, the ZSM-5 molecular sieve of 0-5%, 15-25% diaspore, 2-10% inorganic oxide binder and 20-60% clay composition.

Catalytic cracking three rotation fine powder be by FCC catalyst circulation cracking reaction and regenerative response during because of mechanical wear Or heat the factor such as collapses and forms, its diameter is less than 15um mostly, collect at present it is latter as using the processing mode buried, easily pollute Environment, is also a kind of wasting of resources.

The content of the invention

For above-mentioned produced problem and deficiency, the invention provides a kind of Resid Fcc Catalyst and its preparation side Method.Its matrix of described catalyst is modified by three rotation fine powders, there is suitable gradient pores distribution and suitable acid strong with acid Degree.Slurry oil yield can be greatly lowered, and be obviously improved coke selectivity.To achieve the above objectives, the present invention includes following Step：

A kind of Resid Fcc Catalyst, the catalyst is thin by the rotations of 20-35% REY and 5-25% three by weight Powder catalyst, 15-22% boehmite, 5-12% inorganic oxide binder and 15-30% clay composition. It is characterized in that synthesis step is as follows：

(1) the rotation fine powder catalysts of formula ratio REY and three are beaten with water, use H₃PO₄Its pH value 2.8-3.2 is adjusted, obtains molten Liquid A,

(2) clay of formula ratio, boehmite, inorganic oxide binder are beaten with water, use H₃PO₄Adjust its pH value 2.8-3.2, solution B is obtained,

(3) solution A/solution B cocurrent is added into quick mixing,

(4) mist projection granulating, roasting washing dries prepared catalyst.

The technical indicator of the REY described in step (1) is RE₂O₃It is 10-18wt%, lattice constant is 24.63- 24.75nm。

Step (1) the three rotations fine powder catalyst is by steps of processing：

(1) allotment is with H₂C₂O₄The oxalic acid solution of 60-100g/l is counted,

(2) in oleum being added into the oxalic acid solution in step (1), H is made₂SO₄/H₂C₂O₄Ratio 1-10,

(3) in three rotation fine powder catalysts being added into above-mentioned solution, 60-140 DEG C of controlling reaction temperature, reaction time 1-6 Hour, catalyst/(H₂SO₄+H₂C₂O₄)=1-5,

(4) it is 5-6 to be washed with water to filtrate pH value after completion of the reaction, takes filter cake stand-by.

Boehmite described in step (2) is boehmite, three boehmites, one or more groups of bayerite Close.

Inorganic oxide binder described in step (2) is the mixed of one or more of Alumina gel, Ludox or Alusil Compound.

Clay described in step (2) is kaolin, galapectite, Peng Run are native or the sepiolite mixture of one or more.

Step (1) and step (2) amount of water make mixing rear slurry solid content be 35-37wt%.

The Resid Fcc Catalyst that the above method is prepared.

Compared with prior art, the present invention has the advantage that：

(1) rotation of catalyst three fine powder is realized recycling, and reduces pollution；

(2) after catalyst three revolves fine powder through treatment, there is controllable pore-size distribution to be distributed with acid strength, advantageously reduce oil Slurry yield and improvement catalyst coke selectivity.

(3) introducing of part P elements, further increases the number at catalyst acid center, strengthens slag oil cracking, produces more Many light oils.

Specific embodiment

In order to better illustrate the present invention, with reference to embodiment, the invention will be further described.

The embodiment of the present invention and analysis test assessment method used in comparative example：

(1) chemical composition：Xray fluorescence spectrometer, German Brooker, S8Tiger 3KW.

(2) aperture：Nitrogen adsorption instrument, U.S. Kang Ta, NOVA-E

(3) specific surface：Nitrogen adsorption instrument, U.S. Kang Ta, NOVA-E.

(4) crystallinity：X-ray diffractometer, Rigaku, D/max-3B.

(5) abrasion index：Abrasion index determinator, the permanent loyal machinery in Yueyang.

(6) water hole：Water droplet method

The embodiment of the present invention is raw materials used with comparative example：The raw material that preparation is used is commercially available product, can be with commercially available.

(1) kaolin：Technical grade, China Kaolin Co., Ltd, contents on dry basis 78wt%

(2) boehmite：Technical grade, Shandong Aluminum Co., Ltd. group, alumina content 68wt%

(3) REY molecular sieves：Qingdao Hui Cheng environmental protection Science and Technology Co., Ltd.

(4) three rotation fine powders：Qingdao Hui Cheng environmental protection Science and Technology Co., Ltd.

(5) oleum：Technical grade, commercially available, SO₃Content 60%

(6) phosphoric acid：Technical grade, commercially available, phosphorus pentoxide content 52wt%

(7) oxalic acid：Technical grade, commercially available, concentration of oxalic acid 65g/L

(8) Alumina gel：It is commercially available, alumina content 22.0%

(9) hydrochloric acid：It is commercially available, concentration of hydrochloric acid 37%

Embodiment 1：

The treatment of three rotation fine powder catalysts：

(1) with H₂C₂O₄The oxalic acid solution 10L of 80g/l is counted,

(2) by 800g oleums add oxalic acid solution in, H₂SO₄/H₂C₂O₄Ratio is 1:1,

(3) in three rotation fine powder catalyst 9000g being added into above-mentioned solution, 98 DEG C of controlling reaction temperature, the reaction time 2.5 is small When,

(4) it is 5.6 to be washed with water to filtrate pH value after completion of the reaction, is denoted as SX-1.

Three rotation fine powder catalyst water mashing, uses H after the REY of butt 32% and butt 22% are processed₃PO₄Adjust its pH value 3.0, obtain solution A.

The kaolin of butt 19%, the boehmite of butt 18%, the Alumina gel of butt 9% are beaten mixing and beaten with water Slurry, uses H₃PO₄Its pH value 3.0 is adjusted, solution B is obtained.

The butt of solution A+solution B is 1000g, and solid content is 36%.

Solution A/solution B cocurrent adds quick mixing.

Mist projection granulating, roasting washing dries prepared catalyst CAT-1.

Embodiment 2：

The treatment of three rotation fine powder catalysts：

(1) with H₂C₂O₄The oxalic acid solution 10L of 80g/l is counted,

(2) by 3200g oleums add oxalic acid solution in, H₂SO₄/H₂C₂O₄Ratio is 4:1,

(3) in three rotation fine powder catalyst 9000g being added into above-mentioned solution, 110 DEG C of controlling reaction temperature, the reaction time 4 is small When,

(4) it is 5.6 to be washed with water to filtrate pH value after completion of the reaction, is denoted as SX-2.

The REY of butt 32% and the rotation fine powder catalyst of butt 22% 3 are beaten with water, H is used₃PO₄Its pH value 3.0 is adjusted, is obtained To solution A,

The kaolin of butt 19%, the boehmite of butt 18%, the Alumina gel of butt 9% are beaten mixing and beaten with water Slurry, uses H₃PO₄Its pH value 3.0 is adjusted, solution B is obtained.

The butt of solution A+solution B is 1000g, and solid content is 36%.

Solution A/solution B cocurrent adds quick mixing.

Mist projection granulating, roasting washing dries prepared catalyst CAT-2.

Embodiment 3：

The treatment of three rotation fine powder catalysts：

(1) with H₂C₂O₄The oxalic acid solution 10L of 80g/l is counted,

(2) by 800g oleums add oxalic acid solution in, H₂SO₄/H₂C₂O₄Ratio is 1:1,

(3) in three rotation fine powder catalyst 9000g being added into above-mentioned solution, 140 DEG C of controlling reaction temperature, the reaction time 2 is small When,

(4) it is 5.6 to be washed with water to filtrate pH value after completion of the reaction, is denoted as SX-3.

The REY of butt 28% and the rotation fine powder catalyst of butt 18% 3 are beaten with water, H is used₃PO₄Its pH value 3.0 is adjusted, is obtained To solution A.

The kaolin of butt 20%, the boehmite of butt 22%, the Alumina gel of butt 12% are beaten with water and mixed Mashing, uses H₃PO₄Its pH value 3.0 is adjusted, solution B is obtained.

The butt of solution A+solution B is 1000g, and solid content is 36%.

Solution A/solution B cocurrent adds quick mixing.

Mist projection granulating, roasting washing dries prepared catalyst CAT-3.

Comparative example：

The spraying slurry of 1000g butts is prepared by solid content 36%

(1) add 500g deionized waters to be well mixed the Alumina gel of butt 10%, add the kaolin of butt 40% to beat Slurry.

(2) 32% REY, stirring reaction 0.5 hour are added to above-mentioned slurries.

(3) add the deionized water of 300g to the slurries in (2), add the boehmite of butt 18%, stir.

(4) HCL solution is added to be acidified according to sour aluminum ratio 0.055 in the slurries for stirring.

(5) catalyst slurry that will be acidified is spray-dried, and is washed and is dried, and obtains catalyst DB -1.

The analysis result of three rotation fine powder catalyst SX-1, SX-2 and SX-3 is as follows after being processed in example

Table 1

Spraying catalyst CAT-1, catalyst CAT-2, catalyst CAT-3, catalyst DB-1 analysis results are as follows in example

Table 2

As can be seen that there is silica higher using three rotation fine powder catalysts after present invention acidifying from table 1, table 2 Content and larger average pore size, contrast contrast medium after synthetic catalyst, show specific surface and larger pore volume higher, have It is adapted to big pore size distribution during heavy oil macromolecular is cracked in advance.

Catalyst is aging：The catalyst that will be prepared is standby after hydro-thermal process 17h under 800 DEG C, 100% water vapor conditions.

Evaluating catalyst：The evaluation of catalyst carries out evaluation on FFB is fixed fluidized bed to be carried out.Feedstock oil chooses Lu Qingshi Change mixed material oil, raw material oil nature is shown in Table 3.Reaction temperature is 520 DEG C, and oil ratio is 4.95, catalyst inventory 180g, heavy oil Air speed 20h^-1, evaluation result is shown in Table 4.

The feedstock property of table 3. (the clear petrochemical industry mixed material oil in Shandong).

Table 4.FFB small fixed flowing bed evaluation results.

As can be seen from Table 4, the catalyst for being prepared with the inventive method is compared with the catalytic cracking reaction of comparative example, its product Product heavy oil, the reduction of coke proportion, light oil yield proportion increase, cracking gasoline octane number are slightly elevated.

Although above-mentioned be described to specific embodiment of the invention, not to the limit of the scope of the present invention System, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not pay The various modifications or deformation made by going out creative work are still within protection scope of the present invention.

Claims (7)

1. a kind of Resid Fcc Catalyst, the catalyst revolves fine powder by 20-35% REY and 5-25% three by weight Catalyst, 15-22% boehmite, 5-12% inorganic oxide binder and 15-30% clay composition.Its It is characterised by that synthesis step is as follows：

(1) the rotation fine powder catalysts of formula ratio REY and three are beaten with water, use H₃PO₄Its pH value 2.8-3.2 is adjusted, solution A is obtained,

(2) clay of formula ratio, boehmite, inorganic oxide binder are beaten with water, use H₃PO₄Adjust its pH value 2.8- 3.2, solution B is obtained,

(3) solution A/solution B cocurrent is added into quick mixing,

(4) mist projection granulating, roasting washing dries prepared catalyst.

2. a kind of Resid Fcc Catalyst according to claim 1, it is characterised in that：Plan described in step (2) is thin Diaspore is boehmite, three boehmites, the one or more combination of bayerite.

3. a kind of Resid Fcc Catalyst according to claim 1, it is characterised in that：It is inorganic described in step (2) Adhesive oxides are the mixture of one or more of Alumina gel, Ludox or Alusil.

4. a kind of Resid Fcc Catalyst according to claim 1, it is characterised in that：Clay described in step (2) It is the mixture of one or more of kaolin, galapectite, Peng Run soil or sepiolite.

5. a kind of Resid Fcc Catalyst according to claim 1, it is characterised in that：REY's described in step (1) Technical indicator is RE₂O₃It is 10-18wt%, lattice constant is 24.63-24.75nm.

6. a kind of Resid Fcc Catalyst according to claim 1, it is characterised in that：Step (1) three rotation is thin Powder catalyst is by steps of processing：

(1) allotment is with H₂C₂O₄The oxalic acid solution of 60-100g/l is counted,

(2) in oleum being added into the oxalic acid solution in step (1), H is made₂SO₄/H₂C₂O₄Ratio 1-10,

(3) in three rotation fine powder catalysts being added into above-mentioned solution, 60-140 DEG C of controlling reaction temperature, 1-6 hours reaction time, Catalyst/(H₂SO₄+H₂C₂O₄)=1-5,

(4) it is 5-6 to be washed with water to filtrate pH value after completion of the reaction, takes filter cake stand-by.

7. a kind of Resid Fcc Catalyst according to claim 1, it is characterised in that：Step (1) and step (2) add Water makes solid content be 35-37wt%.