CN104888816B - A kind of aluminium trichloride solid-supported catalyst ebullated bed process units - Google Patents

Abstract

The present invention relates to aluminium trichloride solid-supported catalyst process units field, a kind of more particularly to aluminium trichloride solid-supported catalyst ebullated bed process units.The technical scheme is that：N2 gas Jing N2 effusion meters are entered in CCl4 storage tanks, CCl4 saturated vapor is carried as carrier gas with N2 to enter in AlCl3 generators, with Al2O3 reaction generate AlCl3 gases, AlCl3 gas Jing coolers enter fluidized bed reactor in, with ebullated bed in suspending carrier carry out it is immobilized；Gas interior circulation method is adopted in fluidized bed reactor, is made AlCl3 in ebullated bed interior circulation, reaction is fully contacted with carrier granular, finally the N2 gas containing a small amount of AlCl3, through AlCl3 catchers, entering air after washing the AlCl3 for removing residual；Aluminium trichloride solid-supported catalyst stores stand-by after collecting.The present invention is easy to industrialized production, the problems such as can not only efficiently solving equipment corrosion, environmental pollution and separate difficulty with product, and has the advantages that reaction temperature is low, immobilized rate is high, it is uniform to support.

Description

A kind of aluminium trichloride solid-supported catalyst ebullated bed process units

Technical field

The present invention relates to aluminium trichloride solid-supported catalyst process units composition and preparation technology field, more particularly to one Plant aluminium trichloride solid-supported catalyst ebullated bed process units and preparation technology.

Background technology

Aluminum chloride has extensive purposes as friedel-craft catalysts, is urging for chemical industry, petroleum refining and pharmacy One of agent, its reaction to alkylation, acylation, alkane isomerization, cracking and polymerization show excellent catalytic performance, but The corrosivity of the catalyst are separated difficult with product and to use generation a large amount of useless compared with strong and aftertreatment technology is more complicated Water causes environmental pollution, unbecoming with the theory of clean manufacturing, and its application is increasingly subject to limit.

In order to solve this problem, people start always by AlCl₃It is immobilized, keeping AlCl₃The premise of good characteristic Under so as to it is transformed into environment amenable catalyst.AlCl₃Immobilized research was had made great progress at nearly 30 years, domestic Various aluminium trichloride solid-supported catalyst preparation technologies, such as patent of invention are invented outward：USP2.927.087（1960）, USP4.306.105（1981）, CN 1324690A（2001）、CN1939590A（2007）、CN102247885（2011）、 CN03894225A（2014）Deng.

The common feature of above-mentioned patented technology is by gaseous state AlCl₃Use N₂Being carried in the catalyst carrier of fixed bed is carried out It is immobilized.As fixed bed be present：Such as solid particle poor heat transfer, bed temperature is uneven, AlCl₃In fixed bed carrier Upper diffusion is difficult, and hot-spot causes hydroxyl loss and carrier crystal form to change etc., thus results in catalyst prod and supports low, product Quality can not be guaranteed, therefore the supported catalyst technology of fixed bed is difficult to industrialized production.

For the problems referred to above, the invention provides the ebullated bed process units and system of a kind of aluminium trichloride solid-supported catalyst Standby technique, for realizing the industrialized production of aluminium trichloride solid-supported catalyst.With the device and the supported AlCl of technique₃ The problems such as catalyst can not only efficiently solve equipment corrosion, environmental pollution and separate difficulty with product, and supported AlCl₃For nanostructured, have the advantages that reaction temperature is low, immobilized rate is high, it is uniform to support.Aluminium trichloride solid-supported catalyst Extensively apply, huge economic benefit and environmental benefit will be produced, meet the requirement of current recycling economy development.

The content of the invention

It is an object of the invention to provide a kind of can be given birth to the ebullated bed of industrialized production aluminium trichloride solid-supported catalyst Produce device and preparation technology.

To overcome prior art problem, the invention provides a kind of aluminium trichloride solid-supported catalyst ebullated bed production dress Put, including N₂Effusion meter, CCl₄Storage tank, the AlCl with heater₃Generator, cooler, fluidized bed reactor and AlCl₃ Catcher；N₂Effusion meter and CCl₄Storage tank connects, CCl₄Storage tank and AlCl₃Generator connects, AlCl₃Generator is connected with cooler Connect, cooler is connected with fluidized bed reactor bottom, at the top of fluidized bed reactor and AlCl₃Catcher connects；Ebullating bed reactor Device includes：Cyclone separator, inner circulating tube, catalyst discharging opening, immobilized ebullated bed；Immobilized ebullated bed is arranged on ebullated bed The bottom of reactor, cyclone separator are arranged at fluidized bed reactor top, and inner circulating tube one end is connected with cyclone separator, separately One end causes fluidized bed reactor inner bottom part, and catalyst discharging opening is located on the wall of fluidized bed reactor side；Heater is inductance Heater；Immobilized ebullated bed includes impeller, motor, sieve aperture cone Compound Distribution plate, and impeller together with motor connection, bore by sieve aperture Bluk recombination distribution grid is arranged on above impeller；Thermostat is set below impeller；The structure of sieve aperture cone Compound Distribution plate includes cone Body and sieve aperture, some cones are distributed on Compound Distribution plate, and some sieve apertures are distributed around cone；Cyclone separator and inner circulating tube Constitute AlCl₃Gas internal circulation system.

The invention provides a kind of aluminium trichloride solid-supported catalyst ebullated bed process for producing, process is N₂Through N₂ Effusion meter enters CCl₄In storage tank, with N₂CCl is carried for carrier gas₄Saturated vapor enters AlCl₃In generator, with Al₂O₃Heating is anti- AlCl should be generated₃Gas, AlCl₃Gas enter fluidized bed reactor in, with ebullated bed in suspending carrier carry out it is immobilized, Gu AlCl is collected after loadization₃Solid-supported catalyst.Gas interior circulation method is adopted in fluidized bed reactor, AlCl is made₃In ebullated bed Circulation, is fully contacted reaction with carrier granular, containing a small amount of AlCl₃N₂Gas, through AlCl₃Catcher, then removed by washing The AlCl of residual₃Air is entered after gas；Al₂O₃The temperature of reacting by heating is 400 ~ 500^oC。

The invention has the beneficial effects as follows：The invention provides a kind of ebullated bed production dress of aluminium trichloride solid-supported catalyst Put and preparation technology, using N₂Direct airborne CCl₄Method, the cost of equipment and maintenance cost of dosing pump, and tolerance can be reduced Uniform and stable, operation and maintenance is convenient.Cone and sieve aperture Compound Distribution plate, it is ensured that different size of solid particle is in ebullated bed All in suspended state in space, it is to avoid the deposition of oversized particles and excessively short grained effusion, AlCl is made₃On the carrier particles To preferably immobilized.Using inductive heater temperature control, can solve the problems, such as that particulate matter poor heat transfer, temperature distributing disproportionation are even. With heating quality it is uniform, firing rate is fast, power is big, temperature adjusting high precision the characteristics of.AlCl₃Gas is in ebullating bed reactor Can be recycled in device.AlCl can be improved₃The service efficiency of gas, improves the immobilized rate of carrier.

The present invention is used for the industrialized production for realizing aluminium trichloride solid-supported catalyst.It is supported with the device and technique AlCl₃The problems such as catalyst can not only efficiently solve equipment corrosion, environmental pollution and separate difficulty with product, and carried on a shoulder pole The AlCl of load₃For nanostructured, have the advantages that reaction temperature is low, immobilized rate is high, it is uniform to support.

Description of the drawings

Fig. 1 is a kind of schematic diagram of aluminium trichloride solid-supported catalyst ebullated bed process units；

Fig. 2 is the top view of the hardened structure of sieve aperture cone Compound Distribution.

In figure：1、N₂Effusion meter, 2, CCl₄Storage tank, 3, AlCl₃Generator, 4, inductive heater, 5, cooler, 6, constant temperature Device, 7, sieve aperture cone Compound Distribution plate, 8, fluidized bed reactor, 9, cyclone separator, 10, inner circulating tube, 11, catalyst discharging Mouthful, 12, impeller, 13, motor, 14, A lCl₃Catcher, 15, cone, 16, sieve aperture, 17, entrance.

Specific embodiment

The implementation process of the present invention is further illustrated below in conjunction with the accompanying drawings.Following non-limiting examples can make this area Those of ordinary skill be more fully understood the present invention, but limit the present invention never in any form.

Embodiment 1

Load 0.5 Kg γ-Al in fluidized bed reactor₂O₃(60-80 mesh) carrier, preferred diplopore γ-Al₂O₃(60-80 Mesh), high pure nitrogen passes through N₂Effusion meter (1) enters CCl with the flow of 0.4 L/min₄Basin (2), N₂Carry CCl₄Gas, Jing Pipeline enters AlCl₃Generator（3）.AlCl₃Generator（3）Built with γ-Al₂O₃1.0 Kg, by being enclosed within AlCl₃Generator（3） On inductive heater（4）Control AlCl₃Generator（3）Interior reaction temperature reaches 450^oC。CCl₄With Al₂O₃Reaction is generated AlCl₃Gas, condensed device（5）After cooling, into fluidized bed reactor（8）Bottom, fluidized bed reactor（8）The constant temperature of bottom Device（6）Temperature control is 300^oC。

By motor（13）Impeller（12）The air-flow that at a high speed rotation is produced is by AlCl₃Gas is by through thermostat（6） With cone sieve aperture Compound Distribution plate（7）, with the γ-Al for suspending₂O₃(60-80 mesh) carrier is fully contacted carries out immobilized reaction. Fluidized bed reactor（8）Interior employing gas interior circulation method, i.e., still unreacted AlCl₃From cyclone separator side wall entrance（17）Enter Enter cyclone separator（9）, Jing cyclone separator（9）Separate, still unreacted AlCl₃Into inner circulating tube（10）, through constant temperature Device（6）Return fluidized bed reactor（8）Bottom, by motor（13）Impeller（12）The air-flow that rotation is produced at a high speed again will AlCl₃By cone sieve aperture Compound Distribution plate（7）, immobilized reaction is carried out into fluidized bed reactor and carrier granular, so Iterative cycles.Reaction was stopped operation after 1 hour.Finished catalyst after immobilized is by catalyst discharging opening（11）Release, finished product is urged Agent sealed storage.After testing, AlCl in solid-supported catalyst₃Loading reach 6.2%.

Finally contain a small amount of AlCl₃N₂Gas, through AlCl₃Catcher（14）, residual is thoroughly being removed by washing AlCl₃After enter air.

Claims (4)

1. a kind of aluminium trichloride solid-supported catalyst ebullated bed process units, it is characterised in that：Including N₂Effusion meter, CCl₄Storage tank, AlCl with heater₃Generator, cooler, fluidized bed reactor and AlCl₃Catcher；N₂Effusion meter and CCl₄Storage tank Connection, CCl₄Storage tank and AlCl₃Generator connects, AlCl₃Generator is connected with cooler, cooler and fluidized bed reactor bottom Portion connects, at the top of fluidized bed reactor and AlCl₃Catcher connects；Fluidized bed reactor includes：Cyclone separator, interior circulation Pipe, catalyst discharging opening, immobilized ebullated bed；Immobilized ebullated bed is arranged on the bottom of fluidized bed reactor, cyclone separator Fluidized bed reactor top is arranged at, inner circulating tube one end is connected with cyclone separator, and the other end is caused in fluidized bed reactor Bottom, catalyst discharging opening be located at fluidized bed reactor side wall on, the heater be inductive heater, the immobilized boiling Rising bed includes impeller, motor, sieve aperture cone Compound Distribution plate；Impeller and motor connection, sieve aperture cone Compound Distribution plate are arranged on Above impeller.

2. a kind of aluminium trichloride solid-supported catalyst ebullated bed process units according to claim 1, it is characterised in that：Institute State.

3. a kind of aluminium trichloride solid-supported catalyst ebullated bed process units according to claim 1, it is characterised in that：Institute The structure for stating sieve aperture cone Compound Distribution plate includes cone and sieve aperture, and some cones are distributed on Compound Distribution plate, around cone It is distributed some sieve apertures.

4. a kind of aluminium trichloride solid-supported catalyst ebullated bed process units according to claim 1, it is characterised in that：Institute State cyclone separator and inner circulating tube constitutes AlCl₃Gas internal circulation system.