CN108080009A - A kind of alkane isomerization reaction-regenerative device and method - Google Patents

Abstract

An alkane isomerization reaction-regeneration device, including a reaction device and a regeneration device, the reaction device and the regeneration device are respectively connected through a catalyst regeneration inclined tube and a catalyst standby inclined tube, wherein the regeneration device includes a catalyst regeneration section and a regeneration settling section , the regeneration settling section is located on the upper part of the catalyst regeneration section, and an external circulation pipe is arranged outside the regeneration settling section and the catalyst regeneration section. One end of the external circulation pipe is connected to the regeneration settling section, and the other end is connected to the catalyst regeneration section. The isomerization catalyst used in this device For non-noble metal catalysts. The device has simple and compact structure, flexible and convenient operation, and high production efficiency. In the catalyst external circulation pipe of the regeneration unit and the heat coil exchanger, the axial temperature difference of the regenerator can be effectively reduced, the efficiency of catalyst regeneration can be improved, and energy can be saved.

Description

A kind of alkane isomerization reaction-regeneration device and method

technical field

The invention relates to an alkane isomerization reaction-regeneration device for alkane isomerization, in particular to a circulating fluidized bed alkane isomerization reaction-regeneration device and method.

Background technique

Under the current energy situation, the efficient utilization of alkanes has become a subject of much concern in the petrochemical industry. Taking butane as an example, the total amount of butane in my country in 2014 was 9.54 million tons, of which 3.27 million tons of n-butane, only about 12% of n-butane was used to prepare maleic anhydride, and the rest was used as civil liquefied gas. And isobutane can be used to prepare isobutene, propylene oxide and alkylated gasoline. In the past two years, isobutane dehydrogenation and alkylation have developed rapidly. With the successive commissioning of new facilities, isobutane may be in short supply. Therefore, converting n-butane to isobutane will help to solve the current situation of excess n-butane and the possible shortage of isobutane.

The alkane isomerization catalysts currently used in industry all introduce noble metal Pt or Pd as the "dehydrogenation-hydrogenation" active component, and adopt a fixed-bed isomerization process. The industrial application of this noble metal catalyst is limited by two aspects: on the one hand, the introduction of noble metal greatly increases the preparation cost of the catalyst, and on the other hand, the noble metal component requires extremely high pretreatment of raw materials. In order to achieve long-term stable operation of the fixed bed, the n-paraffin raw material must undergo strict desulfurization, dearsenic and dehydration treatment. UOP's Butamer process requires that the content of sulfur-containing compounds and water in the raw material be less than 1ppm. Even so, there is still the problem of the loss of active component chlorine during the reaction process. US5157199, US 6495733 B1, US 6184430 B1, CN 103814003A and CN1094995A have reported Pt (Pd) modified SO ₄ ^2- -ZrO ₂ catalyst, although this catalyst solves the problem of active component loss, but in order to prolong the regeneration of catalyst Period, the reaction needs to be carried out under the condition of hydrogen. The introduction of hydrogen slows down the deactivation rate of the catalyst at the expense of the isomerization activity of the catalyst, and also increases the operating cost.

The alkane isomerization reaction is a mild exothermic reaction, and the reaction temperature is generally 120-300°C. For the use of some existing catalysts, the regeneration temperature should not be too high, otherwise the catalyst will be partially decomposed, which will not only affect the stability of the catalyst, but also cause the emission of pollutants in the flue gas to exceed the standard. Using a relatively low regeneration temperature, in order to ensure that the catalyst can be fully regenerated, the regeneration time must be moderately extended. In addition, the scheme proposed by CN201610522918.1 still has many unsatisfactory features. The present invention optimizes and improves the scheme proposed in CN201610522918.1, so as to ensure that the device built according to the proposed scheme can operate safely, stably and at low cost, and reduce the discharge of pollutants as much as possible.

In view of this, the present application is proposed.

Contents of the invention

An object of the present invention is to provide an alkane isomerization reaction-regeneration device, which has a simple and compact structure, flexible and convenient operation, and high production efficiency.

An object of the present invention is to provide an alkane isomerization reaction method, which is suitable for the isomerization reaction of C ₄ -C ₇ alkane, and the isomerization reaction has high selectivity and high conversion rate.

Another object of the present invention is to provide a catalyst regeneration reaction method, which can effectively reduce the axial temperature difference of the regeneration device and improve the efficiency of catalyst regeneration.

For realizing the purpose of the present invention, adopt following technical scheme:

An alkane isomerization reaction-regeneration device, including a reaction device and a regeneration device, the reaction device and the regeneration device are respectively connected through a catalyst regeneration inclined tube and a catalyst standby inclined tube, wherein,

The regeneration device includes a catalyst regeneration section and a regeneration settling section. The regeneration settling section is located on the upper part of the catalyst regeneration section. An external circulation pipe is arranged outside the regeneration settling section and the catalyst regeneration section. One end of the external circulation pipe is connected to the regeneration settling section, and the other end is connected to the catalyst regeneration section. part.

A preparation method for alkane isomerization, comprising the steps of:

(1) The raw material enters the dense-phase fluidized reaction section of the reaction device through the feed inlet, and isomerization reaction occurs in contact with the catalyst. The temperature of the dense-phase fluidized section is 50-350°C. The average residence time is between 0.5 and 120 minutes;

(2) The catalyst after the alkane isomerization reaction enters the catalyst regeneration device from the bottom of the reaction device, and the product gas after the reaction carries the catalyst into the catalyst settling section for separation to obtain the isomerization product;

Wherein, the reaction device is a variable-diameter or equal-diameter tank body, and the tank body is divided into a gas stripping section, a reaction section and a catalyst settling section from bottom to top, and the reaction section is a cylindrical structure with an equal diameter.

On the one hand, the active component of the catalyst is one or a mixture of two or more of phosphate, sulfate, tungstate and molybdate, and the carrier includes SiO ₂ , ZrO ₂ , Nb ₂ O ₅ , ZnO, Ga ₂ A mixed oxide or composite oxide formed of one or more of O ₃ and MgO, and the binder is one or two of kaolin, pseudo-boehmite and silica sol.

A catalyst regeneration reaction method, (1) the catalyst regeneration reaction is carried out in the regeneration section of the regeneration device under the condition of a temperature of 350-750° C., and the catalyst stays in the regeneration section on average The time is controlled within 1-120min; preferably, the average temperature in the regeneration section is between 400-550°C; the average superficial gas velocity in the regenerator should be controlled between 0.1-2m/s;

(2) Under the promotion of flue gas, the catalyst in the regeneration section enters the settling section, wherein, part of the high-temperature catalyst entering the settling section returns to the regeneration section through the external circulation pipe for regeneration. Preferably, the amount of part of the high-temperature catalyst is the catalyst in the regeneration device. more than 5% of the total.

Compared with the prior art, the advantages of the present application are:

The alkane isomerization reaction-regeneration device of the present application has simple and compact structure, flexible and convenient operation, high production efficiency, can effectively reduce the axial temperature difference of the regeneration device, and improve the efficiency of catalyst regeneration; the isomerization reaction of the present application adopts non-precious metal active Catalyst with high isomerization selectivity. In particular, the combination of the isomerization reaction device of the present application with the catalyst regeneration device cannot efficiently improve the regeneration efficiency of the catalyst, and can efficiently activate the active components of the non-metallic active catalyst, so that the catalyst can be used efficiently.

Description of drawings

Fig. 1 is an embodiment of the alkane isomerization reaction-regenerating device of the present application.

Detailed ways

The preparation method of the alkane isomerization reaction of the present invention and its corresponding device are further described in detail below. The protection scope of the present application is not limited, and the protection scope is defined by the claims. Certain disclosed specific details provide a thorough understanding of the various disclosed embodiments. However, one skilled in the relevant art will recognize that embodiments may be practiced without one or more of these specific details, and with other materials and the like.

Unless the context requires otherwise, in the specification and claims, the terms "comprising" and "comprising" should be interpreted as an open and including meaning, that is, "including, but not limited to".

The "embodiment", "an embodiment", "another embodiment" or "certain embodiments" mentioned in the specification refer to the described specifically related features and structures related to the embodiment or characteristics are included in at least one embodiment. Thus, "an embodiment," "an embodiment," "another embodiment," or "certain embodiments" are not necessarily all referring to the same embodiments. Furthermore, the particular features, structures or characteristics may be combined in any manner in one or more embodiments. Each feature disclosed in the specification can be replaced by any alternative feature that can serve the same, equivalent or similar purpose. Therefore, unless otherwise specified, the disclosed features are only general examples of equivalent or similar features.

A preparation method for alkane isomerization, comprising the steps of:

(1) The raw material enters the dense-phase fluidized reaction section of the reaction device through the feed inlet, and isomerization reaction occurs in contact with the catalyst. The temperature of the dense-phase fluidized section is 50-350°C, and the average The residence time is 0.5~120min;

(2) The catalyst after the alkane isomerization reaction enters the catalyst regeneration device from the bottom of the reaction device, and the reacted product carries the catalyst into the catalyst settling section for separation to obtain the isomerization product;

Wherein, the reaction device is a variable-diameter or equal-diameter tank body, and the tank body is divided into a gas stripping section, a reaction section, and a catalyst settling section from bottom to top, and the reaction section is an equal-diameter cylindrical structure;

The active component of the catalyst is one or a mixture of phosphate, sulfate, tungstate and molybdate, and the carrier includes SiO ₂ , ZrO ₂ , Nb ₂ O ₅ , ZnO, Ga ₂ O ₃ , A mixed oxide or composite oxide formed by one or more than two kinds of MgO, and the binder is one or two of kaolin, pseudo-boehmite and silica sol.

In certain embodiments, the temperature of the dense phase fluidization section is 150-200°C.

In some embodiments, the average residence time of the catalyst in the dense-phase fluidized reaction zone is 1.0-20 minutes. On the one hand, in the dense-phase fluidized reaction section, the average superficial gas velocity is 0.01-2 m/s, preferably, the average superficial gas velocity is 0.04-1.0 m/s.

On the one hand, the mass space time is 0.1-100h, preferably between 1-10h.

In this application, the mass space time refers to the ratio of the mass of the catalyst in the reactor to the mass of the alkane feed per hour.

The stripping medium of the stripping section of the reaction device can use water vapor, nitrogen, other inert gases and dry gases, and nitrogen is preferably used as the stripping medium.

The raw material includes normal alkanes with 4-7 carbon atoms, such as n-butane, n-pentane and/or n-hexane.

There are other components in the reaction device to ensure more efficient completion of the isomerization reaction.

In some embodiments, a gas stripping medium distributor is provided at the lower end of the gas stripping section; preferably, a loop pipe distributor with nozzles is used.

In some embodiments, a baffle, preferably a herringbone baffle, is provided above the gas stripping medium distributor in the gas stripping section. This setting can improve the effect of the gas stripping medium displacing oil and gas from the pores of the catalyst, and improve the gas stripping efficiency.

There is a feed inlet at the bottom of the reaction section, and the raw materials can be sprayed into the reactor directly through nozzles, or can be fed through a ring pipe with several nozzles.

In order to promote the full contact reaction between the raw material and the catalyst, a grid or a distribution plate is arranged on the upper part of the feed inlet in the dense phase fluidized reaction section. Preferably, the distance between two adjacent layers of grids or distribution plates is 10cm-2m; more preferably 5cm-50cm.

An oil and gas outlet is arranged on the top of the catalyst settling section of the reaction device, and a cyclone separator is arranged in the settling section, wherein the cyclone separator is connected with the oil and gas outlet.

The catalyst in this application is an environment-friendly non-precious metal isomerization catalyst.

In some embodiments, the content of the active component in the catalyst is 0.5-50 wt.%, preferably 2-20 wt.%. The content of the active components is calculated based on the highest valence oxide.

In certain embodiments, the content of the carrier in the catalyst is between 30-99.5 wt.%, preferably 50-91 wt.%.

In some embodiments, the content of the binder in the catalyst is between 0 and 69wt.%, preferably, the content of the binder in the catalyst is greater than 0 and less than or equal to 69wt.%wt.%, More preferably, the content of the binder in the catalyst is 2-46wt.%. The content of the binder is calculated based on the highest valence oxide.

In some embodiments, the binder includes Al ₂ O ₃ and/or silica sol.

In certain embodiments, the isomerization active sites in the n-paraffin isomerization catalyst are generated on the surface of the support by sulfuric acid, metatungstic acid or/and phosphomolybdic acid. Therefore, the active component of the normal paraffin isomerization catalyst is one or a mixture of two or more of phosphate, sulfate, tungstate and molybdate. Preferably, the active component of the n-paraffin isomerization catalyst is sulfate, or a mixture of sulfate and one or more of phosphate, sulfate, tungstate and molybdate. More preferably, the active component of the n-paraffin isomerization catalyst is sulfate.

In some embodiments, the support includes ZrO ₂ , or a mixture thereof with one or more of SiO ₂ , Nb ₂ O ₅ , ZnO, Ga ₂ O ₃ , and MgO.

The catalyst of the present application adopts the method for preparing catalyst commonly used in the prior art, for example, including: (1) mixing the inorganic acid or inorganic acid ammonium salt of the active component with a carrier and a binding agent to obtain a n-paraffin isomerization catalyst (2) the precursor slurry is dried, calcined, pulverized to obtain an isomerization catalyst, or a spray granulation method is used to obtain a normal paraffin isomerization catalyst.

The alkane isomerization catalyst regeneration device provided in this application includes a catalyst regeneration section and a regeneration settling section. The regeneration settling section is located above the catalyst regeneration section, and an external circulation pipe is arranged between the regeneration settling section and the catalyst regeneration section.

The external circulation pipe refers to a pipeline arranged outside the regeneration settling section and the catalyst regeneration section and communicated with the regeneration settling section and the catalyst regeneration section.

With the setting of the external circulation pipe, part of the catalyst drawn from the regeneration settling section is circulated back to the bottom of the regeneration section through the external circulation pipe, further reducing the axial temperature difference of the regeneration reaction device.

The regeneration temperature of the non-metallic catalyst for alkane isomerization of the present application should not be too high, otherwise the catalyst will be partially decomposed, which will affect the stability of the catalyst. To ensure that the catalyst can be fully regenerated, the regeneration time must be moderately extended. However, when the regeneration temperature is not high, by adding an external circulation pipe outside the regeneration device, the regeneration efficiency of the catalyst can be effectively improved, and the active components will not be lost significantly. In other words, the regenerated catalyst has a high content of active components and can be better recycled into the next isomerization reaction, ensuring high selectivity and high conversion rate of the isomerization reaction.

In certain embodiments, one end of the external circulation pipe is connected to the lower side of the catalyst regeneration section, and the other end is connected to the lower side of the regeneration settling section.

The lower part of the regeneration settling section is connected with the regeneration inclined pipe, and the regeneration inclined pipe is provided with a section of vertical heat exchanger near the regeneration settling section, and the axial direction of the vertical heat exchanger and the regeneration settling section set in parallel.

The heat exchanger can be a shell-and-tube heat exchanger, or other forms of heat exchangers. A coil heat exchanger is preferred.

A vertical heat exchanger is installed between the regeneration device and the isomerization reaction device, and the regenerated catalyst coming out of the regeneration inclined tube is exchanged with the reaction raw material or other refrigerants in the heat exchanger, and the heat of the regenerated catalyst is used to transfer the heat of the regenerated catalyst to the reaction The reaction raw materials of the device are preheated, and the temperature of the regenerated catalyst can also be reduced. Before the regenerated catalyst enters the reaction device, the temperature needs to be reduced to 100-350°C, preferably to 200-300°C. Make full use of their own energy to achieve energy saving effect.

The refrigerant can be water, heat transfer oil, liquefied gas, propane and butane, etc.

The stripping medium also needs to be introduced into the heat exchanger to lift the flue gas carried by the catalyst back to the settling section of the regeneration unit. The stripping medium can be water vapor, nitrogen and other inert gases, preferably nitrogen.

Another effect of using a coil heat exchanger is that the flue gas carried by the catalyst can be lifted back to the regeneration unit with a small amount of stripping medium. And the regenerated agent gas lift is integrated with the heat exchanger, and the heat exchange effect between the gas lift and the catalyst and the heat extraction medium is improved by using the fluidization effect of the gas lift and the redistribution effect of the heat exchange coil on the catalyst and the gas lift. The structure of the device is simplified.

The lower part of the catalyst regeneration section is connected with the inclined pipe for preparing catalyst.

The alkane isomerization catalyst regeneration device provided in the present application can be used in combination with all isomerization reaction devices in the prior art. Especially when used in combination with the isomerization reaction device provided by the present application, the entire device has a simple and compact structure, flexible and convenient operation, and high production efficiency.

Utilize the catalyst regeneration method of above-mentioned alkane isomerization catalyst regeneration device, comprise:

(1) The catalyst to be born, high-temperature air or high-temperature flue gas containing oxygen are subjected to regeneration reaction in the regeneration section of the regeneration device at a temperature of 350-750°C, and the average residence time of the catalyst in the regeneration section is controlled at 1-120min.

(2) Under the promotion of flue gas, the catalyst in the regeneration section enters the settling section, wherein, part of the high-temperature catalyst entering the settling section returns to the regeneration section through the external circulation pipe for regeneration. Preferably, the amount of part of the high-temperature catalyst is the catalyst in the regeneration device. More than 5% of the total amount, preferably, the amount of part of the high-temperature catalyst is 10-60% of the total amount of the catalyst in the regeneration device.

In some embodiments, the high-temperature catalyst in the external circulation pipe is returned to the bottom of the section, and regenerated with the catalyst in the regeneration section again.

In this application, the temperature of high-temperature air or oxygen-containing high-temperature flue gas is controlled at 350°C to 750°C.

In certain embodiments, the average temperature in the regeneration section is between 400°C and 550°C.

In certain embodiments, the average residence time of the catalyst in the dense-phase regeneration section of the regeneration section is controlled at 3-40 minutes.

In order to ensure that the temperature in the regenerator is as uniform as possible, the average superficial gas velocity in the dense-phase regeneration section of the regenerator should be controlled between 0.1-2m/s, preferably between 0.5-1.5m/s.

The upper part of the regeneration section is a section of reduced-diameter conveying section, which extends into the settlement section. The diameter of the reduced-diameter conveying section is determined according to the gas velocity. The average superficial gas velocity in the conveying section should be >2m/s, preferably >5m/s.

In order to promote the full contact regeneration of air and catalyst, in some cases, a grid or distribution plate is provided in the upper part of the feed inlet in the regeneration section. Preferably, the distance between adjacent grids or distribution plates is 10cm-2m, preferably 15cm-50cm.

Like other regeneration devices in the prior art, the settling section of the regeneration device is provided with a cyclone separator, and the top is provided with a flue gas outlet, and the outlet of the cyclone separator is connected with the flue gas outlet at the top of the regeneration device. Used to recover catalyst and separate flue gas.

Example 1

This embodiment refers to accompanying drawing 1, and the isomerization reaction device provided by the present application is used in conjunction with the isomerization catalyst regeneration device provided by the present application. These two sets of devices can be used separately, respectively with other reaction devices of the prior art or The catalyst regeneration unit is used in combination.

The isomerization reaction device shown in accompanying drawing 1 is the tank body of variable diameter or equal diameter, and tank body is divided into stripping section 14, reaction section 1 and catalyst settling section 8 from bottom to top, and reaction section 1 is equal diameter Cylindrical structure. The top of the settling section is provided with an oil and gas outlet 13, and a cyclone separator 10 is provided inside to recover the catalyst carried by the oil and gas, and the outlet of the cyclone separator 10 is connected with the oil and gas outlet 13.

The reaction device is respectively connected with the regeneration device through the inclined pipe 17 for raw material and the inclined pipe 18 for regeneration. The regeneration device is a variable diameter or equal diameter tank, including a regeneration section 9 and a regeneration settling section 11. The regeneration settling section 11 is located on the upper part of the catalyst regeneration section 9, and an external circulation pipe 16 is provided outside the regeneration settling section 11 and the catalyst regeneration section 9. , that is, on the outside of the regeneration device, one end of the external circulation pipe is connected to the regeneration settling section 11, and the other end is connected to the catalyst regeneration section 9. The top of the settling section 11 of the regeneration device is provided with a flue gas outlet 12, and a cyclone separator 10 is provided inside to recover the catalyst. The outlet of the cyclone separator is connected with the flue gas outlet 12 at the top of the regenerator.

The upper part of the regenerating section 9 of the regenerator device is a constricted conveying section 15, and the said constricted conveying section 15 extends into the settling section. transverse diameter. A baffle plate is provided above the uppermost end of the conveying section 15 with reduced diameter.

One end of the inclined pipe 17 to be born is connected to the bottom of the stripping section 14 of the reaction device, and the other end of the inclined pipe 17 to be born is connected to the bottom of the regeneration section 9 of the regeneration device; one end of the inclined pipe 18 of the regeneration is connected to the reaction section 1, and the other end is connected to Settling section 11 is regenerated. A heat exchanger 2 is additionally provided between the regeneration inclined pipes 18 . In this embodiment, the heat exchanger 2 is a vertical coil heat exchanger, the coil flows to get the heat medium (or it can be called refrigerant), and the outside of the coil in the heat exchanger is from the regenerative settlement The heat from the device regenerates the catalyst and the flue gas carried.

Sliding valves for controlling the flow rate of the catalyst are arranged on the inclined pipe 17 to be raw and the inclined pipe 18 to regenerate.

A gas stripping medium distributor 6 is provided at the lower end of the gas stripping section 14 of the reaction device, preferably a loop pipe distributor with nozzles. A herringbone baffle 19 is arranged above the gas stripping medium distributor in the gas stripping section 14 . The bottom of the reaction section 1 is provided with a feed port 4, and the raw materials are fed through a ring pipe with several nozzles. In the dense-phase fluidized reaction section, a grid or a distribution plate 5 is arranged on the upper part of the feed inlet, and the distance between adjacent grids or distribution plates is 10cm-2m, preferably 15cm-50cm.

In the regeneration section 9, a grid or a distribution plate 5 is provided on the top of the feed inlet, and the distance between adjacent grids or distribution plates is 10cm to 2m to establish a layer, preferably 15cm to 50cm.

The process of device reaction in the present embodiment comprises:

The raw material enters the dense-phase fluidized reaction section through the feed loop 4, and the catalyst is transported to the reaction section through the stripping medium water vapor, nitrogen, other inert gas or/and dry gas in the stripping section, and the raw material in the reaction section Contact with catalyst and isomerization reaction takes place. The raw material is normal alkanes with 4-7 carbon atoms, preferably n-butane, n-pentane and n-hexane. The isomerization catalyst is an environment-friendly non-precious metal isomerization catalyst disclosed in CN201610522918.1. Nitrogen is preferably used as the stripping medium in the dense-phase fluidized reaction section.

The catalyst to be born in the reaction device enters the regeneration section of the regeneration device through the bottom of the stripping section through the inclined pipe to be produced, and the high-temperature air 7 (can be generated by heating and heat exchange, or directly inject fuel into the The oxygen-containing high-temperature flue gas produced by the combustion furnace) enters the regeneration section 9 from the bottom of the regeneration section through the distributor (to ensure that the air is evenly distributed in the radial direction), and the high-temperature air contacts and reacts with the catalyst to be regenerated in the regeneration section. Then the catalyst in the regeneration section enters the regeneration settling section, and more than 5% of the catalyst enters the regeneration section through the external circulation pipe, and is regenerated by contacting with high-temperature air again. The catalyst in the regeneration settling section carries the flue gas into the regeneration inclined pipe, passes through the heat exchanger, and exchanges heat with the heat-taking medium or raw material in the heat exchanger, reduces the temperature of the regenerated catalyst and enters the isomerization reaction through the regeneration inclined pipe within the paragraph. The heat extraction medium can be water, heat transfer oil, liquefied petroleum gas, propane and butane, etc. The stripping medium 3 needs to be introduced into the heat exchanger to lift the flue gas carried by the catalyst back to the settling section of the regenerator. The stripping medium can be water vapor, nitrogen and other inert gases, preferably nitrogen.

Adopt the alkane isomerization reaction device of the present application to run continuously for 1 month. The results show that the isomerization catalyst has a good reaction-regeneration condition, the catalyst is stable, no significant loss of active components occurs, the loss of active components is less than 0.2%, and the emission of pollutants in the flue gas meets the standard. At the same time, the heat carried by the high-temperature regenerated catalyst is also used to generate high-pressure steam, saving energy consumption.

Example 2

Preparation of isomerization catalyst:

Add 64.62 g of deionized water to 4.85 g of pseudo-boehmite (alumina content of 68 wt.%), stir well in a water bath at 65° C., add 25.85 g of hydrochloric acid to form a gel, and continue stirring. Weigh 100g of _ZrO2 and add it to the prepared gel, stir evenly, add 6.00g of concentrated sulfuric acid and stir for 1h, add 3.00g of phosphoric acid and continue stirring for 1h. Dry at 110°C for 10 hours, then calcined at 650°C for 2 hours, after cooling, crush and sieve, and take 80-180 mesh particles to obtain the final alkane isomerization catalyst.

The non-metallic alkane isomerization catalyst prepared as in Example 2 was used in the alkane isomerization reactions in the following Examples 3-11.

Example 3

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-butane feed is 4.5h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.09m/s. The isomerization reaction temperature is 200° C., and the feed rate of n-butane is 0.8 kg/h. The preheating temperature of regeneration air is 550°C, the superficial gas velocity in the regenerator is 1.5m/s, the regeneration temperature is 550°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 4

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-butane feed is 1.8h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.09m/s. The isomerization reaction temperature is 160° C., and the feed rate of n-butane is 1.6 kg/h. The preheating temperature of the regeneration air is 580°C, the superficial gas velocity in the regenerator is 1.8m/s, the regeneration temperature is 580°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 5

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-butane feed is 6h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.13m/s. The isomerization reaction temperature is 200° C., and the feed rate of n-butane is 0.4 kg/h. The preheating temperature of regeneration air is 450°C, the superficial gas velocity in the regenerator is 1.5m/s, the regeneration temperature is 450°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 6

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-butane feed is 6h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.13m/s. The isomerization reaction temperature is 200° C., and the feed rate of n-butane is 0.8 kg/h. The preheating temperature of regeneration air is 500°C, the superficial gas velocity in the regenerator is 2.5m/s, the regeneration temperature is 500°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 7

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-butane feed is 3.3h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.16m/s. The isomerization reaction temperature is 220° C., and the feed rate of n-butane is 2.0 kg/h. The preheating temperature of regeneration air is 500°C, the superficial gas velocity in the regenerator is 2m/s, the regeneration temperature is 500°C, and the superficial gas velocity in the reducing section is 5m/s.

Example 8

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-pentane feed is 5h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.13m/s. The isomerization reaction temperature is 200° C., and the feed rate of n-pentane is 0.8 kg/h. The preheating temperature of regeneration air is 500°C, the superficial gas velocity in the regenerator is 2.5m/s, the regeneration temperature is 500°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 9

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-pentane feed is 2.5h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.16m/s. The isomerization reaction temperature is 220° C., and the feed rate of n-pentane is 2.0 kg/h. The preheating temperature of regeneration air is 500°C, the superficial gas velocity in the regenerator is 2m/s, the regeneration temperature is 500°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 10

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-hexane feed is 5h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.13m/s. The isomerization reaction temperature is 200° C., and the feed rate of n-hexane is 0.8 kg/h. The preheating temperature of regeneration air is 500°C, the superficial gas velocity in the regenerator is 2.5m/s, the regeneration temperature is 500°C, and the superficial gas velocity in the reducing section is 3m/s.

Example 11

Referring to accompanying drawing 1, implement according to the above-mentioned process of alkane isomerization, specifically, 4 layers of grids are set in the reactor 1. The mass space time of n-hexane feed is 2.5h. The superficial gas velocity of the gas in the reaction section under actual reaction conditions is 0.16m/s. The isomerization reaction temperature is 220° C., and the feed rate of n-hexane is 2.0 kg/h. The preheating temperature of regeneration air is 500°C, the superficial gas velocity in the regenerator is 2m/s, the regeneration temperature is 500°C, and the superficial gas velocity in the reducing section is 3m/s.

Table 1. Example 3-7 n-butane isomerization product distribution (wt.%)

Table 2. Example 8-11 n-pentane, n-hexane isomerization product distribution (wt.%)

Claims (10)

1. A kind of alkane isomerization reaction-regeneration device, comprises reaction device and regeneration device, and reaction device and regeneration device are respectively connected by catalyst regeneration inclined pipe, catalyst waiting for raw inclined pipe, wherein, The regeneration device includes a catalyst regeneration section and a regeneration settling section. The regeneration settling section is located on the upper part of the catalyst regeneration section. An external circulation pipe is arranged outside the regeneration settling section and the catalyst regeneration section. One end of the external circulation pipe is connected to the regeneration settling section, and the other end is connected to the catalyst regeneration section. part; Preferably, one end of the external circulation pipe is connected to the lower side of the catalyst regeneration section, and the other end is connected to the lower side of the regeneration settling section. 2. alkane isomerization reaction-regeneration device according to claim 1, is characterized in that, on the regeneration inclined pipe, a heat exchanger is arranged, Preferably, the heat exchanger is arranged at a position close to the regeneration device; More preferably, the heat exchanger is a vertical heat exchanger, and the vertical heat exchanger is parallel to the regenerative settling section in the axial direction; more preferably, the heat exchanger is a coil heat exchanger. 3. The alkane isomerization reaction-regeneration device according to claim 1 or 2, characterized in that, the reaction device is a tank body with variable diameter or equal diameter, and the tank body is divided into gas stripping sections from bottom to top , a reaction section and a catalyst settling section, the reaction section is a cylindrical structure with equal diameters. 4. The alkane isomerization reaction-regeneration device according to any one of claims 1-3, characterized in that, on the regeneration section top is a section of reduced-diameter conveying section, and this reduced-diameter conveying section stretches into the settling section, shrinking The ratio of the diameter of the diameter section to the diameter of the reaction section is less than 1/1 and greater than or equal to 1/4. 5. A method for isomerization utilizing the alkane isomerization reaction-regeneration device described in any one of claims 1-4, comprising the steps of: (1) The raw material enters the dense-phase fluidized reaction section of the reaction device through the feed inlet, and isomerization reaction occurs in contact with the catalyst. The temperature of the dense-phase fluidized section is 50-350°C. The average residence time is between 0.5 and 120 minutes; (2) The catalyst after the alkane isomerization reaction enters the catalyst regeneration device from the bottom of the reaction device, and the reacted product carries the catalyst into the catalyst settling section for separation to obtain the isomerization product; Wherein, the active component of the catalyst is one or a mixture of two or more of phosphate, sulfate, tungstate, and molybdate, and the carrier includes SiO ₂ , ZrO ₂ , Nb ₂ O ₅ , ZnO, Ga ₂ O _3. A mixed oxide or composite oxide formed of one or more kinds of MgO, and the binder is one or two of kaolin, pseudo-boehmite and silica sol. 6. The preparation method according to claim 5, characterized in that, in the dense-phase fluidized reaction section, the average superficial gas velocity is 0.01-2 m/s, preferably, the average superficial gas velocity is 0.04-1.0 m/s /s. 7. The preparation method according to claim 5 or 6, characterized in that the mass space time of the reaction section is 0.1-100 h, preferably between 1-10 h. 8. The preparation method according to any one of claims 1-4, characterized in that, in the dense-phase fluidized reaction section, a grid or a distribution plate is arranged on the upper part of the feed port; preferably, two adjacent layers of grids The distance between grids or distribution plates is 10cm-2m; more preferably 5cm-50cm. 9. A catalyst regeneration method utilizing the alkane isomerization reaction-regeneration device described in any one of claims 1-3, comprising the steps of: (1) Catalyst to be born, high-temperature air or high-temperature flue gas containing oxygen are subjected to catalyst regeneration reaction in the regeneration section of the regeneration device at a temperature of 350-750°C, and the average residence time of the catalyst in the regeneration section is controlled at 1-120min; Preferably, the average temperature in the regeneration section is between 400 and 550°C; the average superficial gas velocity in the regenerator should be controlled between 0.1 and 2m/s; (2) Under the promotion of flue gas, the catalyst in the regeneration section enters the settling section, wherein, part of the high-temperature catalyst entering the settling section returns to the regeneration section through the external circulation pipe for regeneration. Preferably, the amount of part of the high-temperature catalyst is the catalyst in the regeneration device. more than 5% of the total. 10. The catalyst regeneration reaction according to claim 8, characterized in that the average superficial gas velocity in the regeneration section should be controlled between 0.1-2 m/s, preferably between 0.5-1.5 m/s.