CN103769228B

CN103769228B - A kind of preparation method of micro-spherical catalyst carrier

Info

Publication number: CN103769228B
Application number: CN201210408293.8A
Authority: CN
Inventors: 刘杰; 孙素华; 朱慧红; 金浩; 杨光
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2012-10-24
Filing date: 2012-10-24
Publication date: 2016-08-17
Anticipated expiration: 2032-10-24
Also published as: CN103769228A

Abstract

The present invention discloses the preparation method of a kind of micro-spherical catalyst carrier, including dry, the roasting process of raw material kneading process, pelletization, granulate process, full circle process and spheroidal particle；Described granulate process is process 1 ~ 5 minute in the trimmer that material feeding rotating disk is frosted dish after pelletizing, preferably 1 ~ 3 minute；Treatment conditions be rotating disk revolution be 500 ~ 3000 revs/min, preferably 2000 ~ 3000 revs/min；Air quantity is 50 ~ 100m³/ min, preferably 70 ~ 90m³/min.The features such as it is high that the inventive method has production efficiency, catalyst carrier even particle size distribution, good sphericity, wear-resistant.

Description

A kind of preparation method of micro-spherical catalyst carrier

Technical field

The present invention relates to the preparation method of a kind of micro-spherical catalyst carrier, contain especially for mink cell focus especially metal Measure the preparation method that higher residual oil uses the micro-spherical catalyst carrier of moving bed, bubbling bed hydrotreating process.

Background technology

Heavy oil deep processing is to alleviate one of not enough approach of petroleum resources, and heavy-oil hydrogenation technology is to solve heavy oil deeply to add Work most efficient method.Boiling bed residual oil hydrocracking technology have in raw oil strong adaptability, reactor substantially without pressure drop, Uniformity of temperature profile, mass transfer and heat transfer are good, catalyst can add online and discharge, catalyst utilization height, length service cycle, The advantages such as device flexible operation, are the most constantly developed.

Fluidized bed reactor has perfectly mixed reactor and fluidized reactor feature, and therefore reactor should have good power Learn balance, to maintain beds to expand and fluidization uniformity, reach catalytic hydrogenation reaction balance.This just requires that catalyst should There is some special physicochemical property, be relatively strict with as shape of catalyst, particle size and mechanical strength are had, with Meet special use condition.Usually require that catalyst particle diameter is less than 1mm, be beneficial in reactor keep fluidisation shape State.Catalyst granules is one of main material of fluidization process, and the fluidization characteristic of system is had decisive by the characteristic of granule Effect.Research shows, particle diameter and the little granule of density have good mobile performance, can keep the fluidisation shape of stable system State.Fluidization quality is also had an impact by grain shape, and the flow regime of spheroidal particle is best.Additionally, be hydrogenated with at boiling bed residual oil Cheng Zhong, owing to, in fluidized bed reactor, catalyst is in continuous kinestate.Therefore, the wear resistance of catalyst is also One important indicator.Ratio granulometric range 0.2～0.6 mm conveniently is thought in research, the most spherical.Because spheroidal particle is not The most readily flowed, and there is no the corner as sharply easily crashed in other shape.The abrasion of catalyst can be reduced.

At present, the preparation method of industrial spheric catalyst mainly has spray drying forming, forming oil column, rolling molding Deng, but maybe can not prepare 0.2～0.6 mm spheroidal particle, or i.e. enable the spheroidal particle preparing this particle size range, and or yield The lowest, or anti-wear performance is very poor.

CN200710010378.X discloses the preparation method of a kind of micro-spherical catalyst carrier.By catalysis suitable for humidity Agent carrier feed product makes the granule of suitable size, then by this granule spheroidising, round a diameter of 0.1～ 0.8mm, makes spherical carrier of catalyst by round heating.The inventive method can prepare the catalysis of diameter 1mm following microspheroidal Agent or carrier, and production efficiency is high, but the one way preparation time of catalyst carrier is longer, and the sphericity of catalyst carrier is relatively Difference.

CN88102669.7 discloses a kind of method preparing spheroidal particle, and the method includes: by powdery starting material, liquid Body and paraffin kneading form a kneading model group or agglomerated grain.In the case of without extrusion molding, by screening by kneading model roll into a ball or Agglomerated grain isolates the chip of predefined size.Again granule is carried out nodularization in the rotating cylinder of heating.The method can be prepared 0.05 ~ 0.5mmd micro-spherical particle, but preparation efficiency is relatively low.

CN99807621.X discloses a kind of method preparing spherical oxide particles.Raw material is sent into the roller rotated against In, subsequently raw material is delivered on slotted roller, in order to make club, club is cut into the granule of substantial constant length； By so-formed convert globulate thing.The method can produce the spheric catalyst of a diameter of 0.5 ~ 7mm.But the method is real Diameter 2 ~ 5mmd spheroidal particle is suitably prepared on border.

CN201010030842 discloses the preparation method of a kind of spherical aluminum trioxide catalyst carrier.First by SB Powder, additive, surface contain the Properties of Polystyrene Nano Particles of carboxylated hydrophilic group, deionized water and mix making beating by a certain percentage and stir Even, then dropping 5～12mL molar concentrations are the salpeter solution of 10%～50%, the water-bath at 20～90 DEG C is reacted 40～ 350min, prepares colloidal sol, then through oil ammonia column spheroiding particle, and washing, first dry at 30～90 DEG C, then at 200～800 DEG C Lower program roasting 4～6 hours, obtain spherical aluminum trioxide catalyst carrier, and alumina carrier is spherical uniformly, and particle diameter is about 1.6mm.Spherical diameter prepared by the method is relatively big, and owing to using oil, is unfavorable for environmental protection.

US6251832 and US6495488 describes a kind of method preparing spheroidal particle, by aluminium oxide, silicon-aluminum, titanium- Aluminum, zirconium-aluminum etc. make colloidal sol, are subsequently adding many saccharides and form certain density colloidal sol, afterwards with dripping the method for ball by drop Instill in the solution containing polyvalent metal ion, formed spherical.The method also is difficult to prepare the spheroidal particle of below 1mm.

Summary of the invention

For the deficiencies in the prior art, it is an object of the invention to provide the micro-spherical catalyst of a kind of below diameter 1mm The continuous preparation method of carrier.It is high that this method has production efficiency, catalyst carrier even particle size distribution, and good sphericity is wear-resisting The features such as damage.

The preparation method of a kind of micro-spherical catalyst carrier, including raw material kneading process, pelletization, granulate process, whole Circle process and dry, the roasting process of spheroidal particle；Described granulate process be will pelletize after material send into rotating disk be frosted Process 1 ~ 5 minute in the trimmer of dish, preferably 1 ~ 3 minute；Treatment conditions be rotating disk revolution be 500 ~ 3000 revs/min, preferably 2000 ~ 3000 revs/min；Air quantity is 50 ~ 100m³/ min, preferably 70 ~ 90m³/min。

Raw material kneading process described in the inventive method: raw material is added kneading in kneading machine with distilled water etc. and becomes plastic Body, raw material is as a example by boehmite, and butt (alumina weight) content of plastic is generally 32% ~ 43%, preferably 35% ~ 40%, kneading process is the process known to professional and technical personnel in the field.Micro-spherical catalyst carrier raw material can be according to difference Requirement add in the feed suitable auxiliary agent (such as titanium, phosphorus, silicon, boron, zinc, zirconium etc.) and additive (as peptizer, binding agent, One or more in expanding agent etc.).

Pelletization described in the inventive method is the material making kneading under the positive and negative turning effort rotating cylinder, Mandatory make granule by screen cloth face.The big I of particle diameter according to the particle diameter of purpose product by adjusting screen cloth Mesh number realizes.

Full circle process described in the inventive method is to send into the material after granulate in the trimmer that rotating disk is CD to locate Manage 1 ~ 10 minute, preferably 1 ~ 5 minute；Treatment conditions be the revolution of rotating disk be 1000 ~ 3000 revs/min, preferably 1500 ~ 3000 Rev/min；Air quantity is 10 ~ 80m³/min。

Spheroidal particle described in the inventive method be dried, roasting condition as follows: by globular material at 50～120 DEG C It is dried 3～10 hours, constant temperature calcining 1～obtain last micro-spherical catalyst carrier in 4 hours at 400～900 DEG C.Microspheroidal Catalyst carrier pore volume is 0.6 ~ 1.5mL/g, and specific surface area is 120 ~ 320m²/ g, average pore size is 11 ~ 30nm.

Compared with prior art, the inventive method increases granulate process, between granule materials and frosted dish, between granule Under the common effect of the frictional force produced and impact force each other and air, form the shot-like particle that length is of substantially equal Matter.The adhesion that this arrangement process is prevented between granule materials, can directly carry out full circle, and substantially reduce full circle after granulate Time.The method can prepare the spherical carrier of catalyst of diameter 0.1 ~ 2.0mm continuously, is particularly suitable for preparing diameter 0.1 ~ 1mm's Micro-spherical catalyst carrier.The spherical carrier of catalyst prepared has even particle size distribution, production efficiency height, purpose product receipts The advantage such as rate height, product good sphericity, wear resistance are good.

Detailed description of the invention

Illustrate the functions and effects of the inventive method below in conjunction with embodiment, but following example not in pairs this The restriction of bright method.

Embodiment 1

Weigh boehmite 2000g, white carbon black 14g, acetic acid (mass concentration 36%) 28g and water purification 1750g, use kneading machine After mediating as plastic, sending into granulator and pelletize, using screen cloth is 40 mesh.After granulation, the communicated band of material delivers to rotating disk for mill In the trimmer of emery disc, material reaches about 1000g, starts trimmer and carries out granulate, and air quantity is 80m³/ min, rotating disk revolution is 2500 revs/min, the time is 1.5 minutes.Then opening trimmer limit wall discharging opening, it is CD that logical charge tube joins rotating disk Trimmer in spheroidization, air quantity is 55m³/ min, rotating disk revolution is 2000 revs/min, and the time is 3 minutes.By balling-up material It is dried 5 hours at 80 DEG C, 750 DEG C of roastings 3 hours, obtains carrier Z-1, the basic condition of carrier, it is shown in Table 1.

Embodiment 2

In embodiment 1 into, acetic acid is changed ammonia (d_0.95) 42g, water purification changes 1780g into, and other is same as in Example 1, To carrier Z-2, the basic condition of carrier is shown in Table 1.

Embodiment 3

In embodiment 1, water purification changing 1650g into, granulation screen cloth changes 60 mesh into, and granulate air quantity is 72 m³/ min, rotating disk turns Number is 2000 revs/min, and the time is 1 minute, and other is same as in Example 1, obtains carrier Z-3.

Embodiment 4

In embodiment 1, water purification changing 1800g into, granulation screen cloth changes 14 mesh into, and granulate air quantity is 88 m³/ min, rotating disk turns Number is 2800 revs/min, and the time is 2 minutes, and the spheroidization time is 4 minutes.Other is same as in Example 1, obtains carrier Z-4, The basic condition of carrier is shown in Table 1.

Comparative example 1

Take the material identical with example 1, provide spheroidal particle for oneself according to CN200710010378.X method.Granulation screen cloth is 40 Mesh, extrusion granule materials carries out spheroidization after under agitation placing 30 minutes, and rotating disk (CD) revolution is 2000 turns, and air quantity is 66 m³/ min, the time is 20 minutes.Balling-up material is dried 5 hours at 80 DEG C, 750 DEG C of roastings 3 hours, obtains carrier Z-5, carry The basic condition of body is shown in Table 1.

Table 1 catalyst carrier situation

Sample	Z-1	Z-2	Z-3	Z-4	Z-5
						Time (min)	4.5	4.5	4	6	20
Granularity is divided Cloth	40 mesh: 5%, 40 ~ 80 mesh: 92%, 80 mesh: 3%	40 mesh: 4%, 40 ~ 80 mesh: 91%, 80 mesh: 5%	70 mesh: 7%, 70 ~ 110 mesh: 91%, 110 mesh: 2%	15 mesh: 11%, 15 ~ 20 mesh: 85%, 20 mesh: 4%	40 mesh: 3%, 40 ~ 80 mesh 89%, 80 mesh: 9%
						Sphericity	0.896	0.890	0.911	0.886	0.780
Abrasion refers to Number %	0.31	0.34	0.30	0.38	0.62

* particle size distribution uses laser particle analyzer to measure；Sphericity uses Laca light microscope determining；Abrasion index flows Change bed abrasion instrument to measure.Time is the molding time after single batch materials is pelletized to spherical sample.

As can be seen from Table 1, the catalyst carrier prepared by this method, the time used is short, and even particle size distribution, product are received Rate height, product good sphericity, wear resistance are good.

Claims

1. the preparation method of a micro-spherical catalyst carrier, it is characterised in that: include raw material kneading process, pelletization, whole Dry, the roasting process of grain process, full circle process and spheroidal particle；Described granulate process is that the material feeding after pelletizing turns Dish be frosted dish trimmer in process 1 ~ 5 minute；Treatment conditions be rotating disk revolution be 500 ~ 3000 revs/min；Air quantity is 50 ~ 100m³/ min, described full circle process is to send into the material after granulate in the trimmer that rotating disk is CD to process 1 ~ 10 minute； Treatment conditions be the revolution of rotating disk be 1500 ~ 3000 revs/min.

Method the most according to claim 1, it is characterised in that: described granulate process is that the material feeding after pelletizing turns Dish be frosted dish trimmer in process 1 ~ 3 minute；Treatment conditions be rotating disk revolution be 2000 ~ 3000 revs/min；Air quantity is 70 ~90m³/min。

Method the most according to claim 1, it is characterised in that: described raw material kneading process will intend thin water aluminum, distilled water Adding kneading in kneading machine with additive and become plastic, the contents on dry basis of plastic is 32% ~ 43%.

4. according to the method described in claim 1 or 3, it is characterised in that: the contents on dry basis of the plastic of kneading is 35% ~ 40%.

Method the most according to claim 1, it is characterised in that: described pelletization is that the material making kneading is rotating rolling Under the positive and negative turning effort of cylinder, mandatory make granule by screen cloth face.

Method the most according to claim 1 or 5, it is characterised in that: the big I of particle diameter according to purpose product Grain diameter realizes by adjusting the mesh number of screen cloth.

Method the most according to claim 1, it is characterised in that: described full circle process is to send into the material after granulate to turn Dish be CD trimmer in process 1 ~ 5 minute；Treatment conditions be the revolution of rotating disk be 1500 ~ 3000 revs/min.

Method the most according to claim 1, it is characterised in that: described spheroidal particle be dried, roasting condition as follows: will Globular material is dried 3～10 hours at 50～120 DEG C, constant temperature calcining 1～obtain last micro-for 4 hours at 400～900 DEG C Spherical carrier of catalyst.