WO2017125012A1

WO2017125012A1 - Method and system for synchronously recycling biomass and detoxifying chromium slag by using waste heat of blast furnace slag

Info

Publication number: WO2017125012A1
Application number: PCT/CN2017/071515
Authority: WO
Inventors: 张大磊; 袁宪正; 杨新飞; 齐元峰; 路亮; 蔡荣宝
Original assignee: 青岛理工大学
Priority date: 2016-01-19
Filing date: 2017-01-18
Publication date: 2017-07-27
Also published as: CN105598132B; CN105598132A

Abstract

A new method and a system for pyrolysing a biomass and preparing a high-quality fuel gas by using liquid blast furnace slag. By means of process control, the liquid blast furnace slag can be effectively cooled and the heat energy thereof is effectively utilized, and at the same time, the biomass is converted into a high-quality energy gas. The method is: heating the liquid blast furnace slag and gasifying the biomass and cooling water; performing a catalytic reaction on a pyrolysis gas of the biomass and steam under a catalytic action of chromium slag; tar gradually generating an energy gas mainly comprising CO and H₂; and at the same time, Cl₂ and CO₂ in the energy gas being absorbed by an alkaline substance in the chromium slag. The system comprises a granulator, a rotary reaction cooling apparatus, a catalytic reforming furnace and an internal-heated rotary furnace. In the present method and the system, energy is greatly saved during cooling the blast furnace slag, and at the same time, a high-quality energy gas is obtained.

Description

Method and system for simultaneously utilizing blast furnace slag waste heat to simultaneously synthesize biomass and harmless chromium residue

This application claims to be submitted to the Chinese Patent Office on January 19, 2016, the application number is CN201610035340.7, and the Chinese patent application entitled "A Technology for Synchronizing Recycling Biomass and Harmless Chromium Slag Using Blast Furnace Slag Waste Heat" Priority is hereby incorporated by reference in its entirety.

Technical field

The invention is a method for simultaneously processing chromium slag and biomass and cooling the blast furnace slag, and at the same time saving energy, while at the same time obtaining harmless chromium slag and obtaining high-grade energy gas, at the same time. It belongs to the field of environmental protection and low carbon technology.

Background technique

Chromium slag is a by-product of emissions from the production of dichromate. Because it contains water-soluble hexavalent chromium, it is extremely toxic. If it is stored in the open air without treatment, it will cause different degrees of pollution to groundwater sources, rivers or sea areas, and seriously endanger human health and the growth of animals and plants.

In general, the detoxification method of chromium slag (that is, the high toxicity of hexavalent chromium into trivalent chromium) is divided into two categories: wet detoxification and dry detoxification. But they all have their own problems. The wet method is a method of detoxifying Cr ⁶⁺ in a chromium residue in a liquid phase by adding a reducing agent. However, the reagents of this method are expensive and costly, and it is currently difficult to be used for large-scale treatment of chromium slag. Dry detoxification is the purpose of detoxification by reducing the hexavalent chromium in the chromium residue to trivalent chromium by the strong reduction of the high temperature reducing atmosphere. The traditional dry treatment is to use carbon as a reducing agent, and then reduce the toxic Cr ⁶⁺ to non-toxic Cr ³⁺ by heating to about 1000 ° C in a reducing atmosphere. This method has been applied to the treatment of chromium slag on a large scale. Certain economic benefits, but the treatment process is accompanied by secondary dust pollution, and the investment cost is high and the energy consumption is large.

On the other hand, China produces a large amount of biomass every year. Nowadays, most of the biomass is not used effectively, and field burning is carried out, which forms haze and seriously affects the atmospheric environment. Biomass pyrolysis is a biomass utilization method, but its product tar is often difficult to use, and there is also the problem of equipment coking. The patent No. 2014102110190 describes a method for producing fuel gas by using sludge and biomass catalytic reforming and cracking, which converts biomass tar into a combustible gas, although a relatively easy to use fuel gas is produced, but The CO ₂ content is high and the quality is poor. At the same time, the high temperature of about 1000 ° C is needed, the energy consumption is large, and the utilization rate is low; in addition, the method also needs to utilize the relatively expensive CaO-based, A l ₂ O ₃ -based catalyst.

In addition, China produces a large amount of blast furnace slag each year, and the liquid blast furnace slag has a high temperature and a temperature of 1500-1700 ° C. If it can be used well, it will be a valuable resource. However, there are currently few technologies that make efficient use of the heat.

Summary of the invention

In view of the deficiencies of the prior art, the present invention is a novel treatment and disposal method for chromium slag, biomass and liquid blast furnace slag. Through process control, the liquid blast furnace slag can be effectively cooled and its thermal energy can be effectively utilized, while the biomass is converted into high-quality energy gas, and the hexavalent chromium in the chromium slag is efficiently reduced.

The technical scheme of the process is: heating and gasifying the biomass and cooling water by the liquid blast furnace slag, and then using the high temperature catalytic cracking of the biomass cracking gas by the hazardous waste chromium slag, and thoroughly converting the biomass into steam under the condition of steam vaporization. Low-molecular high-temperature energy gases (H ₂ , CO, CH _{4 ,} etc.) avoid coking on the surface of the chromium slag. At the same time, the high-temperature energy gas generated by the biomass heats the chromium residue, and at the same time reduces the hexavalent chromium in the chromium residue to trivalent chromium, and causes the low-temperature chromium residue to cool the energy gas, and the C ₂ and CO in the energy gas. ₂ is absorbed by the alkaline substance in the chromium residue. The process saves energy while harmless chromium residue, and at the same time obtains high-grade energy gas.

The invention provides a method for synchronously utilizing blast furnace slag waste heat to simultaneously recycle biomass and harmless chromium slag, comprising heating liquid biomass and cooling water by using liquid blast furnace slag to generate high temperature mixed gas of biomass cracking gas and water vapor. . The high temperature mixed gas is catalytically reformed with the chromium residue sintered in the catalytic reforming furnace to generate a high temperature energy gas, and the high temperature mixed gas is exchanged with the chromium slag in the internal heat rotary kiln to convert the rotary kiln The hexavalent chromium in the chromium slag is reduced to trivalent chromium.

The method of the present invention specifically includes the following steps:

(1) The liquid blast furnace slag at a temperature of 1500-1700 °C is poured from the slag tank to the inlet end of the granulator. After granulation, it enters the inlet of the rotary reaction cooling device from the outlet end, mixes with the biomass, and pyrolyzes the biomass. Then, the blast furnace slag and the biomass pyrolysis coke are sent to the outlet end of the rotary reaction cooling device, and are discharged after cooling by the cooling water; the continuous input mass ratio of the cooling water and the blast furnace slag for cooling the blast furnace slag is 1: (1-8); The continuous input mass ratio of the material to the blast furnace slag is 1: (1-8).

(2) The cooling water in step (1) is added from the outlet end of the rotary reaction cooling device, and the surface of the blast furnace slag is heated and converted into water vapor; the water vapor is then reversely flowed with the blast furnace slag and exchanged heat, and is sent to the rotary reaction cooling device. The inlet end is mixed with the biomass pyrolysis gas; the mixed gas is then sent to the granulator for heat exchange with the high temperature blast furnace slag, and converted into a high temperature mixture of 800-1400 ° C.

(3) The mixed gas in the step (2) is sent to the catalytic reforming furnace, and the calcined chromium slag is loaded in the furnace, and the chromium slag heated by the mixed gas is catalytically reformed in the range of 800-1200 ° C to generate an energy gas. .

(4) The high-temperature energy gas generated in step (3) is then input into the kiln head of the internal heat rotary kiln, and the chromium slag continuously conveyed from the kiln tail is subjected to heat exchange treatment, and the energy gas reduces the hexavalent chromium in the chromium slag to three. Chromium; after the temperature of the high-temperature energy gas is reduced to below 250 °C, it is discharged from the kiln of the rotary kiln. Into the condensing device, reverse flow with cooling water and indirect heat exchange, condensed and dehydrated and collected; high temperature chromium slag after heat transfer is discharged from the rotary kiln head, enters the cooling device, and is cooled to below 150 °C with cooling water. At the same time, using the generated steam to control the internal pressure of the cooling device is higher than the outdoor air pressure 0-30kp; the mass ratio of the continuously generated high-temperature energy gas to the continuously input chromium slag is controlled at (1-8):4.

(5) The high-temperature chromium slag after heat exchange in step (4) is discharged from the rotary kiln head, enters the cooling device, is cooled by cooling water to below 150 ° C, and is discharged by using the generated steam to control the inside of the cooling device. The air pressure is higher than the outdoor air pressure 0-30kp.

The invention also provides a system for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat, which comprises a granulator, a rotary reaction cooling device, a catalytic reforming furnace, an internal heating rotary furnace, and the granulation a discharge port of the device is connected to the inlet of the rotary reaction cooling device, and a material outlet of the rotary reaction cooling device is in communication with a cooling medium inlet of the granulator, a cooling medium outlet of the granulator and the a furnace head of the catalytic reforming furnace is connected, a tail of the catalytic reforming furnace is in communication with a boring head of the inner-rotating rotary ram, and a cooling water inlet is disposed at an outlet of the rotary reaction cooling device, the inner-rotating type The stern of the shovel is provided with a chromium slag inlet.

Compared with the conventional biomass processing method, the method and system for utilizing blast furnace slag waste heat to simultaneously synthesize biomass and harmless chromium residue have the following advantages:

1. Using high-temperature liquid blast furnace slag to heat and gasify biomass and cooling water to produce biomass cracking products and water vapor, to create conditions for catalyzing the preparation of high-quality energy gas by cracking products; at the same time making full use of heat energy, greatly improving energy efficiency;

2. Using chromium slag hazardous waste chromium slag to catalyze biomass, avoiding the use of expensive catalysts, and achieving the harmlessness of chromium slag;

3. Due to the action of high temperature steam, the chromium content of the chromium residue is greatly reduced after the reduction treatment, which is beneficial to the secondary utilization of the treated chromium residue;

4. The use of high-temperature energy gas generated after catalytic reforming to heat the harmless chromium slag while saving additional equipment for cooling high-temperature gas;

5. Make full use of the water vapor generated in each stage of the process, without additional heat source to assist the production of steam, which is conducive to energy saving, while reducing steam emissions and avoiding secondary heat pollution;

6. The by-product CO ₂ produced in the energy gas generated by biomass catalytic cracking can be absorbed by alkaline substances such as CaO in the chromium residue to improve the quality of the fuel product;

7. Chromium slag cooling equipment uses cooling water to cool the chromium slag, generate steam, increase the internal pressure of the device, prevent external air from entering the system, and redefine the trivalent chromium, while avoiding the use of additional devices to control the air pressure.

DRAWINGS

Figure 1 is a process flow chart

Figure 2 is a schematic diagram of the granulator

1 granulator inlet; 2 cracking gas and water vapor inlet; 3 cracking gas and water vapor outlet; 4 blast furnace slag granulation outlet; 5 rotating disk.

detailed description

Example 1

Referring to Figure 1, Figure 2, the specific embodiment is as follows:

S1, using liquid blast furnace slag to heat gasification biomass and cooling water to produce a high temperature mixture of biomass cracking gas and water vapor.

Specifically, the following detailed steps are included:

(1) The liquid blast furnace slag at a temperature of 1500 ° C is poured from the slag tank into the granulator inlet 1 , and after granulation, it enters the inlet of the rotary reaction cooling device from the outlet end, mixes with the biomass, and pyrolyzes the biomass. Subsequently, the blast furnace slag and the biomass pyrolysis coke are sent to the outlet end of the rotary reaction cooling device, and are discharged after cooling by the cooling water; the continuous input mass ratio of the cooling water and the blast furnace slag for cooling the blast furnace slag is 1:2; the biomass and the blast furnace slag The continuous input mass ratio is 1:2;

It should be noted that biomass will produce a large amount of tar during gasification, and its composition is very complicated. More than 200 kinds of components can be analyzed, mainly including more than 20 kinds, most of which are benzene derivatives and polycyclic aromatic hydrocarbons. (PAH), of which 7 are contained in an amount of more than 5%, which are benzene, naphthalene, toluene, xylene, styrene, phenol and hydrazine. The tar condenses into a liquid at a low temperature (<200 ° C), and is in a gaseous state as the temperature rises, and can be decomposed into a small molecule permanent gas at a high temperature (not condensed into a liquid when the temperature is lowered). Therefore, the content of tar in the combustible gas decreases as the temperature increases.

The biomass is continuously mixed with the granulated high-temperature blast furnace slag entering the rotary cooling device from the inlet end of the rotary reaction cooling device, and then the high-temperature blast furnace slag is heated and pyrolyzed by the biomass, and the blast furnace slag and biomass after the pyrolysis reaction The coke, the tar mixture, and the like are transported to the outlet end of the rotary cooling device by the rotary transfer mechanism of the rotary cooling device for discharge. And since the transmission process is a rotary transmission, the high-temperature blast furnace slag can be sufficiently mixed and contacted with the biomass and the biomass coke during the transportation process, so that the high-temperature blast furnace slag can continuously heat the pyrolysis unreacted biomass, so that The pyrolysis reaction of biomass is carried out more fully.

(2) The cooling water in step (1) is added from the outlet end of the rotary reaction cooling device, and the surface of the blast furnace slag is heated and converted into water vapor; the water vapor is then reversely flowed with the blast furnace slag and exchanged heat, and is sent to the rotary reaction cooling device. The inlet end is mixed with the biomass pyrolysis gas; the mixed gas is then sent to the granulator for heat exchange with the high temperature blast furnace slag, and converted into a high temperature mixed gas of 1000 ° C;

The cooling water is added through the outlet end of the rotary cooling device, so that the cooling water can cool the high-temperature blast furnace slag and the biomass coke after the pyrolysis reaction is completed, and does not affect the pyrolysis reaction, and at the same time, the cooling water and the high-temperature blast furnace slag And the biomass coke and the like are evaporated into water vapor during the heat exchange process, and the reverse flow of the water vapor and the blast furnace slag are continuously exchanged, and the biomass pyrolysis gas generated after the biomass pyrolysis is mixed to form a high temperature mixed gas from the rotary reaction. The inlet end of the cooling device is discharged into the granulator as a cooling medium. According to the flow rate of the different high temperature mixed gas, the temperature of the high temperature mixed gas after heat exchange with the liquid blast furnace slag at 1500 ° C is 800 ° C. Among them, water vapor provides hydrogen and oxygen for the subsequent catalytic reforming reaction and as a reaction gas for catalytic reforming reaction with biomass pyrolysis gas.

Among them, the liquid blast furnace slag heated and gasified biomass and cooling water continuous input mass ratio of 0.2:1.

S2, catalytically reforming the high-temperature mixed gas with the chromium residue calcined in the catalytic reforming furnace to generate a high-temperature energy gas, and exchanging the high-temperature mixed gas with the chromium residue in the internal heat rotary kiln, The hexavalent chromium in the chromium slag in the rotary kiln is reduced to trivalent chromium.

Specifically, the following detailed steps are included:

(3) The mixed gas in the step (2) in the above step S1 is sent to the catalytic reforming furnace, and the chromium slag after the calcination is loaded in the furnace, and the chromium slag heated by the mixed gas is subjected to catalytic reforming in the range of 800 ° C. Generating energy gas;

It should be noted that the chromium slag supported in the catalytic reforming furnace mainly contains hexavalent chromium, and the chromium slag mainly functions as a catalyst in the catalytic reforming reaction, and the biomass pyrolysis gas and water vapor in the mixed gas are in the chromium. The reforming occurs under the catalysis of the slag, and a high-temperature energy gas in which a gas such as H ₂ , CO, and CH _{4 is} mixed is generated.

(4) The high-temperature energy gas generated in step (3) is then input into the kiln head of the internal heat rotary kiln, and the chromium slag continuously conveyed from the kiln tail is subjected to heat exchange treatment, and the energy gas reduces the hexavalent chromium in the chromium slag to three. Chromium; after the temperature of the high-temperature energy gas is reduced to below 250 °C, it is discharged from the kiln of the rotary kiln, enters the condensing device, flows backward with the cooling water and indirectly exchanges heat, collects after condensation and dehydration; The high-temperature chromium slag is discharged from the rotary kiln head, enters the cooling device, is cooled by cooling water to below 150 ° C, and is discharged by using the generated steam to control the internal pressure of the cooling device equal to the outdoor air pressure; the continuously generated high-temperature energy gas The mass ratio to the continuously input chromium slag is controlled at 2:1;

It should be noted that the chromium slag input from the tail of the internal heat rotary raft is the same as the chromium slag contained in the catalytic reforming furnace, but the chrome residue containing hexavalent chromium is different from the catalytic reforming furnace. The chromium slag in the crucible is continuously input continuously, which is opposite to the transportation direction of the high-temperature energy gas entering the internal heating crucible. The energy gas discharged from the tail of the rotary kiln enters the condensing device, flows backward with the cooling water and undergoes indirect heat exchange, and is collected after condensation and dehydration, in order to remove the water generated in the reduction reaction, thereby contributing to the improvement of the quality of the energy gas.

(5) The high-temperature chromium slag after heat exchange in step (4) is discharged from the rotary kiln head, enters the cooling device, is cooled by cooling water to below 150 ° C, and is discharged by using the generated steam to control the inside of the cooling device. The air pressure is equal to the outdoor air pressure;

It is to be noted that the high-temperature chromium slag after the heat exchange is cooled by the cooling water to generate a large amount of water vapor, so that the residual heat can be fully utilized, and the water vapor can be used in other processes. In addition, the use of the generated steam to control the internal pressure of the cooling device is equal to the outdoor air pressure, which is beneficial to the airtightness of the pipeline, the prevention of external air entering the pipeline system, and the transportation of water vapor.

(6) Using the GB5086.2 horizontal oscillation method to carry out the toxicity leaching test on the treated chromium residue, the measured water-soluble chromium is 0.01mg/L, which is much lower than the national standard GB5085.3 upper limit of hazardous waste 1.5mg/L; The substance produces 0.6 energy gas, and the combustible gas content is higher than 80%.

Referring to FIG. 1, the embodiment further provides a system for synchronously utilizing blast furnace slag waste heat to simultaneously recycle biomass and harmless chromium slag, including a granulator, a rotary reaction cooling device, a catalytic reforming furnace, and an internal heat recovery. In the converter, the discharge port of the granulator is connected to the inlet of the rotary reaction cooling device, and the material outlet of the rotary reaction cooling device is connected with the cooling medium inlet of the granulator, and the cooling medium outlet of the granulator is The furnace head of the catalytic reforming furnace is connected, the tail of the catalytic reforming furnace is connected with the head of the internal rotary type rotary raft, and the outlet of the rotary reaction cooling device is provided with a cooling water inlet, and the tail of the inner rotating type rotary shovel is provided with chromium. Slag import.

Referring to Fig. 2, the inside of the granulator has a rotating disc 5 for reacting with the liquid blast furnace slag to granulate the liquid blast furnace slag. One end of the granulator is provided with a granulator inlet 1, and the liquid blast furnace slag is granulated. At the inlet 1 of the vessel, the granulator is introduced, and the granulator is further provided with a cracking gas and a steam inlet 2 and a cracking gas and a steam outlet 3 for the cooling medium to enter and exit. The cracking gas and water vapor exchange heat with the liquid blast furnace slag entering the granulator. The bottom of the granulator is further provided with a blast furnace slag granulation outlet 4, and blast furnace slag formed by granulation in the granulator is discharged from the blast furnace slag granulation outlet 4.

Example 2:

(1) The liquid blast furnace slag at a temperature of 1700 ° C is poured from the slag tank into the granulator inlet 1 , and after granulation, it enters the inlet of the rotary reaction cooling device from the outlet end, mixes with the biomass, and pyrolyzes the biomass. Subsequently, the blast furnace slag and the biomass pyrolysis coke are sent to the outlet end of the rotary reaction cooling device, and are discharged after cooling by the cooling water; the continuous input mass ratio of the cooling water and the blast furnace slag for cooling the blast furnace slag is 1:4; the biomass and the blast furnace slag The continuous input mass ratio is 1:2;

(2) The cooling water in step (1) is added from the outlet end of the rotary reaction cooling device, and the surface of the blast furnace slag is heated and converted into water vapor; the water vapor is then reversely flowed with the blast furnace slag and exchanged heat, and is sent to the rotary reaction cooling device. The inlet end is mixed with the biomass pyrolysis gas; the mixed gas is then sent to the granulator for heat exchange with the high temperature blast furnace slag, and converted into a high temperature mixture gas of 1400 ° C;

The cooling water is added through the outlet end of the rotary cooling device, so that the cooling water can cool the high-temperature blast furnace slag and the biomass coke after the pyrolysis reaction is completed, and does not affect the pyrolysis reaction, and at the same time, the cooling water and the high-temperature blast furnace slag And the evaporation of water, such as biomass coke, is evaporated into water. Gas, reverse flow of water vapor and blast furnace slag continue to exchange heat and mix with biomass pyrolysis gas generated after biomass pyrolysis, and form high-temperature mixed gas discharged from the inlet end of the rotary reaction cooling device into the granulator as a cooling medium, according to different The flow rate of the high-temperature mixture gas is 1400 ° C after heat exchange with the liquid blast furnace slag at 1700 ° C. Among them, water vapor provides hydrogen and oxygen for the subsequent catalytic reforming reaction and as a reaction gas for catalytic reforming reaction with biomass pyrolysis gas.

Among them, the liquid blast furnace slag heated and gasified biomass and cooling water continuous input mass ratio of 5:1. (3) The mixed gas in the step (2) is sent to the catalytic reforming furnace, the chromium slag after the calcination is loaded in the furnace, and the chromium slag heated by the mixed gas is catalytically reformed in the range of 800 ° C to generate an energy gas;

(4) The high-temperature energy gas generated in step (3) is then input into the kiln head of the internal heat rotary kiln, and the chromium slag continuously conveyed from the kiln tail is subjected to heat exchange treatment, and the energy gas reduces the hexavalent chromium in the chromium slag to three. Chromium; after the temperature of the high-temperature energy gas is reduced to below 250 °C, it is discharged from the kiln of the rotary kiln, enters the condensing device, flows backward with the cooling water and indirectly exchanges heat, collects after condensation and dehydration; The kiln head is discharged, enters the cooling device, and is cooled by using cooling water to be cooled to below 150 ° C. At the same time, the generated water vapor is used to control the internal pressure of the cooling device to be higher than the outdoor air pressure by 30 kp; the continuously generated high-temperature energy gas and continuous input The mass ratio of chromium slag is controlled at 1:1;

(5) The high-temperature chromium slag after heat exchange in step (4) is discharged from the rotary kiln head, enters the cooling device, is cooled by cooling water to below 150 ° C, and is discharged by using the generated steam to control the inside of the cooling device. The air pressure is higher than the outdoor air pressure by 30kp;

(6) Using the GB5086.2 horizontal oscillation method to carry out the toxicity leaching test on the treated chromium residue, the measured water-soluble chromium is 0.01mg/L, which is much lower than the national standard GB5085.3 upper limit of hazardous waste 1.5mg/L; The substance produces 0.7t of energy gas with a combustible gas content above 80%.

It should be understood that the temperature of the liquid blast furnace slag may vary, and the temperature of the liquid blast furnace slag may also be 1550 ° C, 1580 ° C, 1600 ° C, 1650 ° C, 1680 ° C or other temperatures. The temperature after heat exchange between the high temperature mixture and the liquid blast furnace slag may be 900 ° C, 1000 ° C, 1100 ° C, 1200 ° C, 1300 ° C or other temperatures. The temperature at which the catalytic reforming is carried out may be selected in addition to 800 ° C in the present embodiment, and other temperatures of 900 ° C, 1000 ° C, 1100 ° C, 1200 ° C or 800-1200 ° C may be selected according to actual process conditions. The continuous input mass ratio of biomass and cooling water heated by liquid blast furnace slag can be 0.3:1, 0.4:1, 0.8:1, 1:1, 2:1, 3:1, 4:1 according to different process conditions. Or other values. The generated water vapor is used to control the internal pressure of the cooling device to be higher than the outdoor air pressure by 10kp, 15kp, 20kp, 25kp or other pressure values. The energy produced per ton of biomass can be 0.65t other values.

The above embodiments are only used to illustrate the technical solutions of the present invention, and are not limited thereto; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still The technical solutions are described as being modified, or equivalents are replaced by some of the technical features; and such modifications or substitutions do not depart from the spirit and scope of the technical solutions claimed in the present invention.

Claims

A method for simultaneously utilizing blast furnace slag waste heat to simultaneously synthesize biomass and harmless chromium slag, characterized in that it comprises the following steps:

(1) The liquid blast furnace slag at a temperature of 1500-1700 °C is poured from the slag tank to the inlet end of the granulator, and after heat transfer granulation, it enters the inlet of the rotary reaction cooling device from the outlet end, mixes with the biomass, and the biomass is Pyrolysis, then blast furnace slag and biomass pyrolysis coke are sent to the outlet end of the rotary reaction cooling device, cooled by cooling water and discharged;

(2) The cooling water in step (1) is added from the outlet end of the rotary reaction cooling device, and the surface of the blast furnace slag is heated and converted into water vapor; the water vapor is then reversely flowed with the blast furnace slag and exchanged heat, and is sent to the rotary reaction cooling device. The inlet end is mixed with the biomass pyrolysis gas; the mixed gas is then sent to the granulator for heat exchange with the liquid blast furnace slag, and converted into a high temperature mixed gas of 800-1400 ° C;

(3) The mixed gas in the step (2) is sent to the catalytic reforming furnace, and the calcined chromium slag is loaded in the furnace, and the chromium slag heated by the mixed gas is catalytically reformed in the range of 800-1200 ° C to generate an energy gas. ;

(4) The high-temperature energy gas generated in step (3) is then input into the kiln head of the internal heat rotary kiln, and the chromium slag continuously conveyed from the kiln tail is subjected to heat exchange treatment, and the energy gas reduces the hexavalent chromium in the chromium slag to three. Chromium; after the temperature of the high-temperature energy gas is reduced to below 250 °C, it is discharged from the kiln at the end of the rotary kiln, enters the condensing device, flows backward with the cooling water and undergoes indirect heat exchange, and collects after condensation and dehydration;

(5) The high-temperature chromium slag after heat exchange in step (4) is discharged from the rotary kiln head, enters the cooling device, is cooled by cooling water to below 150 ° C, and is discharged by using the generated steam to control the inside of the cooling device. The air pressure is higher than the outdoor air pressure 0-30kp.
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to claim 1, characterized in that the continuous input mass ratio of cooling water and blast furnace slag for cooling blast furnace slag is 1: (1) -8).
A method for simultaneously synthesizing biomass and harmless chromium slag using blast furnace slag residual heat according to claim 1, wherein the continuous input mass ratio of biomass to blast furnace slag is 1: (1-8).
A method for simultaneously synthesizing biomass and harmless chromium slag using blast furnace slag residual heat according to claim 1, wherein the mass ratio of the continuously generated high-temperature energy gas to the continuously input chromium slag is controlled (1) -8): 4.
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to claim 1, wherein the continuous input mass ratio of cooling water and biomass for cooling blast furnace slag is controlled at (0.2-) 5): 1.
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to claim 1, characterized in that the chromium residue supported in the catalytic reforming furnace can be dolomite and A l 2 O 3 Substituted nanoscale catalysts.
A method for simultaneously synthesizing biomass and detoxifying chromium slag using blast furnace slag residual heat according to claim 1, wherein the biomass is replaced by a substance containing an organic component such as plastic or sludge.
A method for simultaneously synthesizing biomass and harmless chromium residue by using blast furnace slag waste heat, characterized in that the method comprises the following steps:

Using liquid blast furnace slag to heat gasification biomass and cooling water to produce a high temperature mixture of biomass cracking gas and water vapor;

The high temperature mixed gas is catalytically reformed with the chromium residue sintered in the catalytic reforming furnace to generate a high temperature energy gas, and the high temperature mixed gas is exchanged with the chromium slag in the internal heat rotary kiln to convert the rotary kiln The hexavalent chromium in the chromium slag is reduced to trivalent chromium.
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to claim 8, wherein the liquid blast furnace slag is subjected to heating and gasification of the biomass and the cooling water. Granulation.
The method according to claim 9, wherein the temperature of the liquid blast furnace slag is 1500 to 1700 ° C. The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag residual heat.
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to claim 9, wherein the high temperature mixture is mixed with the chromium residue before catalytic reforming The gas exchanges heat with the liquid blast furnace slag subjected to granulation.
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to claim 11, wherein the temperature of the high temperature mixture after heat exchange with the liquid blast furnace slag subjected to granulation is 800 -1400 ° C.
The method for simultaneously synthesizing biomass and detoxifying chromium slag using blast furnace slag residual heat according to claim 8, wherein the reaction temperature for performing catalytic reforming is 800 to 1200 °C.
A method for simultaneously synthesizing biomass and detoxifying chromium slag using blast furnace slag waste heat according to any one of claims 8 to 13, characterized in that said liquid blast furnace slag heats said biomass and said biomass The continuous input mass ratio of cooling water is (0.2-5):1.
A method for simultaneously synthesizing biomass and detoxifying chromium slag using blast furnace slag waste heat according to any one of claims 8 to 13, characterized in that said liquid blast furnace slag heats said biomass and said biomass The continuous input mass ratio of liquid blast furnace slag is (1-8):1.
A method for simultaneously synthesizing biomass and detoxifying chromium slag using blast furnace slag waste heat according to any one of claims 8 to 13, characterized in that said liquid blast furnace slag is heated and gasified by said cooling water and said said The continuous input mass ratio of the liquid blast furnace slag is 1: (1-8).
The method for synchronously recycling biomass and harmless chromium residue by using blast furnace slag waste heat according to any one of claims 8 to 13, characterized in that it further comprises cooling the high temperature chromium residue generated after catalytic reforming to 150 After being discharged below °C, the water vapor generated by the heat exchange of the high-temperature chromium slag is used to control the air pressure in the cooling device to be higher than the outdoor air pressure of 0-30 kp.
A system for simultaneously synthesizing biomass and harmless chromium slag using blast furnace slag waste heat, characterized in that it comprises a granulator, a rotary reaction cooling device, a catalytic reforming furnace and an internal heat rotary furnace, the granulator a discharge port is connected to the inlet of the rotary reaction cooling device, and a material outlet of the rotary reaction cooling device is in communication with a cooling medium inlet of the granulator, a cooling medium outlet of the granulator and the catalytic weight The burner of the whole furnace is connected, the tail of the catalytic reforming furnace is in communication with the head of the inner-rotating rotary raft, and the rotary reaction cooling device is provided with a cooling water inlet at the outlet thereof, the internal rotation type The stern of the shovel is provided with a chromium slag inlet.