阅读说明：本技术 一种精馏高沸物与电镀废水气化协同处理方法及系统 (Gasification co-processing method and system for rectified high-boiling residues and electroplating wastewater ) 是由 周志江 蔡波 董国君 黄河 吴健 郑小伦 陈锋 陈一菡 于 2020-12-25 设计创作，主要内容包括：本发明公开了一种精馏高沸物与电镀废水气化协同处理方法及系统,系统包括预处理单元、预制浆单元、水煤浆合成单元及气化处理单元；预处理单元包括原料煤预处理单元、精馏高沸物预处理单元、电镀废水预处理单元及活性炭预处理单元；预制浆单元包括第一磨机以及预制浆罐；水煤浆合成单元包括第二磨机和水煤浆罐；气化处理单元包括与水煤浆罐连接的气化炉。本发明通过两段式制浆系统,先将精馏高沸物、电镀废水与活性炭粉末预处理后混合研磨制成预制浆,然后再与煤粉混合研磨制成水煤浆,最后将水煤浆进行气化处理,利用精馏高沸物、电镀废水、活性炭粉末与煤粉之间的配伍作用,提高了制得的水煤浆的性能,从而提高废弃物气化处理效果。(The invention discloses a method and a system for the gasification cooperative treatment of rectified high-boiling residues and electroplating wastewater, wherein the system comprises a pretreatment unit, a prefabricated slurry unit, a coal water slurry synthesis unit and a gasification treatment unit; the pretreatment unit comprises a raw material coal pretreatment unit, a rectification high-boiling residue pretreatment unit, an electroplating wastewater pretreatment unit and an active carbon pretreatment unit; the pre-slurry unit comprises a first mill and a pre-slurry tank; the coal water slurry synthesis unit comprises a second mill and a coal water slurry tank; the gasification treatment unit comprises a gasification furnace connected with the water-coal slurry tank. According to the invention, through a two-stage pulping system, the rectified high-boiling-point substance, the electroplating wastewater and the activated carbon powder are pretreated and then mixed and ground to prepare the pre-pulping, then the pre-pulping is mixed and ground with the coal powder to prepare the coal water slurry, and finally the coal water slurry is gasified, and the performance of the prepared coal water slurry is improved by utilizing the compatibility among the rectified high-boiling-point substance, the electroplating wastewater, the activated carbon powder and the coal powder, so that the gasification treatment effect of wastes is improved.)

1. A gasification cooperative treatment system for rectified high-boiling residues and electroplating wastewater is characterized by comprising a pretreatment unit, a prefabricated slurry unit, a coal water slurry synthesis unit and a gasification treatment unit; the pretreatment unit comprises a raw material coal pretreatment unit (1), a rectification high-boiling-point substance pretreatment unit (2), an electroplating wastewater pretreatment unit and an active carbon pretreatment unit (3) which operate independently, wherein the raw material coal pretreatment unit and the rectification high-boiling-point substance pretreatment unit respectively comprise a storage bin (101), a crushing device (102) and a screening device (103) which are connected in sequence; the activated carbon pretreatment unit comprises a storage bin, an iron remover (301) and a screening device which are connected in sequence; the electroplating wastewater pretreatment unit comprises an electroplating wastewater storage tank (4); the prefabricated slurry unit comprises a first mill (5) and a prefabricated slurry tank (6), a feed inlet of the first mill is respectively connected with screening devices and an electroplating wastewater storage tank in the rectification high-boiling-point substance pretreatment unit and the active carbon pretreatment unit, and a discharge outlet of the first mill is connected with the prefabricated slurry tank; the coal water slurry synthesis unit comprises a second mill (7) and a water coal slurry tank (8), a feed inlet of the second mill is respectively connected with the raw material coal pretreatment unit and the prefabricated slurry tank, and a discharge outlet of the second mill is connected with the water coal slurry tank; the gasification treatment unit comprises a gasification furnace (9) connected with the water-coal slurry tank.

2. The gasification co-processing system for rectification high-boiling residues and electroplating wastewater as claimed in claim 1, wherein the pre-slurry unit further comprises a first water storage tank (10) and a first additive storage tank (11) which are respectively connected with the feed inlet of the first mill; the coal water slurry synthesis unit also comprises a second water storage tank (12) and a second additive storage tank (13) which are respectively connected with the feed inlet of the second mill.

3. The system for the gasification and co-treatment of the rectified high-boiling residue and the electroplating wastewater as claimed in claim 1, wherein the pre-slurry tank and the water-coal slurry tank comprise a tank body (601) and a stirring and cleaning device arranged in the tank body, the top of the tank body is provided with a slurry inlet (602), and the bottom of the tank body is provided with a slurry outlet (603); the stirring and cleaning device comprises a stirring shaft (15) and a stirring paddle (16), wherein one end of the stirring shaft is connected with a driving device arranged at the top of the tank body, the other end of the stirring shaft extends into the bottom in the tank body, the stirring paddle (16) is arranged at one end of the stirring shaft positioned in the tank body, the stirring shaft and the stirring paddle are hollow and communicated, a plurality of spraying openings (17) are formed in the outer wall of the stirring paddle, and a water inlet pipe (18) is sleeved at one end of the stirring shaft positioned; the driving device comprises a driving bevel gear (20) connected with a driving motor (19) and a driven bevel gear (21) in transmission connection with the driving bevel gear, and the driven bevel gear is in transmission connection with the stirring shaft.

4. The system for the gasification and co-treatment of the rectified high boiling substance and the electroplating wastewater as claimed in claim 3, wherein the end of the stirring paddle near the inner wall of the tank body is provided with a side wall brush (22) contacting with the inner wall of the tank body; the bottom of the end of the stirring shaft in the tank body is provided with a bottom brush (23) which is contacted with the bottom of the tank body.

5. The gasification co-processing system for the rectified high boiling residue and the electroplating wastewater as claimed in claim 3, wherein a support frame (604) for placing a driving motor is arranged at the top of the tank body.

6. A method for carrying out gasification cooperative treatment on rectified high boiling residues and electroplating wastewater by using the system as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:

(1) crushing raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal by sieves with different sizes to obtain coal powder with different particle sizes, and mixing the coal powder with different particle sizes to obtain graded coal powder; the rectified high-boiling residue, the activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated high-boiling residue powder, activated carbon powder and electroplating wastewater;

(2) feeding the pretreated high-boiling residue powder, the activated carbon powder and the electroplating wastewater into a pre-pulping unit together for primary grinding and stirring to obtain pre-pulping, wherein the primary grinding time is 10-20 min, and the primary stirring time is 5-20 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with graded coal powder and then is subjected to secondary grinding and stirring to obtain coal water slurry, wherein the secondary grinding time is 20-30 min, and the secondary stirring time is 5-20 min;

(4) and feeding the coal water slurry into a gasification furnace in the gasification treatment unit for combustion.

7. The gasification co-processing method for the rectified high-boiling residue and the electroplating wastewater as claimed in claim 6, wherein the raw coal in the step (1) is crushed in a pretreatment unit, and then is respectively sieved by a 40-60 mesh sieve and a 80-100 mesh sieve, and the mass ratio of the raw coal to the raw coal is 1: (3-4) mixing to obtain the graded coal powder.

8. The gasification co-processing method for the rectified high boiling point substance and the electroplating wastewater as claimed in claim 6 or 7, wherein the rectified high boiling point substance in the step (1) is crushed in a pretreatment unit and then passes through a 60-80 mesh sieve to obtain high boiling point substance powder.

9. The gasification co-processing method for the rectified high boiling point substance and the electroplating wastewater as claimed in claim 6, wherein water and an additive are added in the step (2) and the step (3), and the coal water slurry obtained in the step (3) comprises 70-75 parts by weight of graded coal powder, 15-20 parts by weight of high boiling point substance powder, 5-8 parts by weight of activated carbon powder, 25-35 parts by weight of electroplating water, 35-45 parts by weight of water and 1-2 parts by weight of an additive.

10. The gasification co-processing method of the rectified high boiling residue and the electroplating wastewater as claimed in claim 6 or 9, wherein the activated carbon powder in the step (2) is surface modified activated carbon powder, and the preparation method comprises:

A) adding activated carbon into a nitric acid solution with the mass concentration of 20-50%, wherein the mass volume ratio of the activated carbon to the nitric acid is 1g (20-50 mL), reacting for 2-4 h at 80-90 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 90-110 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding proportion of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g (20-30 mL) to 1-3 g, reacting for 8-10 h under heat preservation, and filtering and washing a product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding proportion of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g (20-30 mL) to (3-5 mL), stirring and reacting for 10-15 h at 60-70 ℃ under the protection of nitrogen, and filtering and washing a product to obtain amino modified activated carbon;

D) adding amino modified activated carbon into ethanol and water in a volume ratio of (3-5): 1, adding chloroacetic acid and sodium bicarbonate into the mixed solvent of 1, wherein the addition ratio of the amino modified activated carbon to the mixed solvent to the chloroacetic acid to the sodium bicarbonate is (1 g, 30-50 mL) to (1-2 g): (1-1.5 g), stirring and reacting for 8-10 h at 55-65 ℃, filtering, washing, drying, grinding and sieving with a 400-600 mesh sieve to obtain the surface modified activated carbon powder.

Technical Field

The invention relates to the technical field of waste treatment, in particular to a method and a system for the gasification cooperative treatment of rectified high-boiling residues and electroplating wastewater.

Background

In the rectification and purification process of organic resin and other substances, a large amount of high-boiling residue is generated at the bottom of a kettle, and the treatment of the rectified high-boiling residue is a difficult problem which troubles manufacturers for many years, and no effective treatment mode exists at present. The quality of the wastewater in the electroplating industry is complex, the wastewater contains heavy metal ions such as chromium, zinc, copper, nickel, cadmium and the like, the COD content is high, the biodegradability is poor, and the effective treatment is difficult to obtain by using the traditional treatment method.

Waste and coal are mixed to prepare coal water slurry, and then the coal water slurry is cooperatively treated by using a coal water slurry gasification furnace, so that the resource utilization and harmless treatment of the waste can be realized, and the method is a brand-new waste treatment mode which is environment-friendly, energy-saving and capable of changing waste into valuable and is widely concerned at present. For example, in the chinese patent document, "a coal water slurry of gasified coal blended with petrochemical waste and a pulping process thereof", which is published under the publication number CN106433822B, the preparation method comprises the following steps: (1) grading of coal powder: drying, crushing, grinding and screening coal to obtain coal powder with different particle size distributions; (2) preparing coal water slurry: coal, petrochemical waste, additives and water are added into a coal grinding system and are mixed and ground into coal water slurry.

If the rectified high boiling residue and the electroplating wastewater can be prepared into the water-coal-slurry, the thorough cleaning of waste disposal and the maximization of resource utilization can be realized. However, when the water-coal-slurry is prepared by using the rectified high-boiling-point substance, the rectified high-boiling-point substance is easy to settle, and the prepared water-coal-slurry has poor stability; because a large amount of heavy metal ions exist in the electroplating wastewater, the existence of the heavy metal ions can also influence the dispersibility and stability of the water-coal-slurry, so that the rectified high-boiling-point substances and the electroplating wastewater are difficult to be effectively prepared into the water-coal-slurry at present, and the gasification synergistic treatment is realized.

Disclosure of Invention

The invention aims to overcome the defects that when the water-coal-slurry is prepared by rectifying high-boiling-point substances in the prior art, the rectified high-boiling-point substances are easy to settle, and the prepared water-coal-slurry has poor stability; the method and the system for the gasification cooperative treatment of the rectified high-boiling-point substance and the electroplating wastewater have the advantages that the rectified high-boiling-point substance, the electroplating wastewater and the active carbon powder are pretreated and then mixed and ground to prepare pre-slurried slurry, then the pre-slurried slurry and the pulverized coal are mixed and ground to prepare the coal water slurry, and finally the coal water slurry is gasified, and the performance of the prepared coal water slurry is improved by utilizing the compatibility among the rectified high-boiling-point substance, the electroplating wastewater, the active carbon powder and the pulverized coal, so that the gasification treatment effect of wastes is improved.

In order to achieve the purpose, the invention adopts the following technical scheme:

a gasification cooperative treatment system for rectified high-boiling residues and electroplating wastewater comprises a pretreatment unit, a prefabricated slurry unit, a coal water slurry synthesis unit and a gasification treatment unit; the pretreatment unit comprises a raw material coal pretreatment unit, a rectification high-boiling-point substance pretreatment unit, an electroplating wastewater pretreatment unit and an active carbon pretreatment unit which are operated independently, wherein the raw material coal pretreatment unit and the rectification high-boiling-point substance pretreatment unit respectively comprise a storage bin, a crushing device and a screening device which are connected in sequence; the activated carbon pretreatment unit comprises a storage bin, an iron remover and a screening device which are connected in sequence; the electroplating wastewater pretreatment unit comprises an electroplating wastewater storage tank; the prefabricated slurry unit comprises a first mill and a prefabricated slurry tank, a feed inlet of the first mill is respectively connected with screening devices and an electroplating wastewater storage tank in the rectification high-boiling-point substance pretreatment unit and the active carbon pretreatment unit, and a discharge outlet of the first mill is connected with the prefabricated slurry tank; the coal water slurry synthesis unit comprises a second mill and a coal water slurry tank, a feed inlet of the second mill is respectively connected with the raw material coal pretreatment unit and the prefabricated slurry tank, and a discharge outlet of the second mill is connected with the coal water slurry tank; the gasification treatment unit comprises a gasification furnace connected with the water-coal slurry tank.

The invention carries out two-stage pulping by a pre-pulping unit and a coal water slurry synthesis unit after the pretreatment of raw material coal, rectified high-boiling residues, active carbon and electroplating wastewater by a pretreatment unit and then by two pulping units: firstly, mixing the rectified high-boiling-point substance pretreated by the waste pretreatment unit, activated carbon powder and electroplating wastewater in a prefabricated slurry unit to enable the three to fully react, adsorbing and removing metal ions in the electroplating wastewater by using the activated carbon powder, and carrying out surface modification on the rectified high-boiling-point substance by using organic components contained in the electroplating wastewater to improve the dispersion performance of the rectified high-boiling-point substance; then the coal water slurry enters a coal water slurry synthesis unit to be mixed with coal powder, and high-performance coal water slurry with high content, good stability and good fluidity is prepared after secondary grinding and stirring; finally, the prepared coal water slurry is sent into a gasification treatment unit for gasification treatment, so that resource utilization and harmless treatment of wastes are realized.

According to the invention, the rectified high-boiling-point substances, the activated carbon, the electroplating wastewater and the coal powder are compatible, the compatibility and the synergistic effect among the wastes are fully utilized, the wastes and the coal powder are modified to prepare the high-performance coal water slurry, and the resource utilization and the harmless treatment of the wastes are realized by matching the wastes with the wastes prepared from wastes; and through the two-stage pulping process, the rectified high-boiling-point substances, the activated carbon and the electroplating wastewater are mixed, ground and stirred firstly, and then mixed with the coal powder for secondary grinding and stirring, so that the wastes can fully react, the mutual compatibility can be effectively exerted, various properties of the prepared waste coal water slurry are improved, the storage and transportation of the coal water slurry are facilitated, the subsequent gasification treatment efficiency is improved, and the treatment effect of the wastes is improved.

Preferably, the pre-pulping unit further comprises a first water storage tank and a first additive storage tank which are respectively connected with the feed inlet of the first mill; the coal water slurry synthesis unit also comprises a second water storage tank and a second additive storage tank which are respectively connected with the feed inlet of the second mill.

Preferably, the precast slurry tank and the coal-water slurry tank comprise tank bodies and stirring and cleaning devices arranged in the tank bodies, slurry inlets are formed in the top of the tank bodies, and slurry outlets are formed in the bottoms of the tank bodies; the stirring cleaning device comprises a stirring shaft and a stirring paddle, wherein one end of the stirring shaft is connected with a driving device arranged at the top of the tank body, the other end of the stirring shaft extends into the bottom in the tank body, the stirring paddle is arranged at one end of the stirring shaft in the tank body, the stirring shaft and the stirring paddle are hollow and communicated, a plurality of spraying openings are formed in the outer wall of the stirring paddle, and a water inlet pipe is sleeved at one end of the stirring shaft, which is positioned outside the tank body; the driving device comprises a driving bevel gear connected with the driving motor and a driven bevel gear in transmission connection with the driving bevel gear, and the driven bevel gear is in transmission connection with the stirring shaft.

In the process of preparing the coal water slurry, wastes are easy to remain on the side wall, the bottom and the stirring device of the tank body, and if the tank body is not cleaned in time after long-time operation, the residual wastes can influence the performance and the quality stability of the prepared coal water slurry. The existing cleaning mode is to spray water into the tank body through a spray pipe so as to achieve the purpose of cleaning, and the cleaning mode is inconvenient to operate and difficult to clean. The invention sets stirring and cleaning devices which can play a role of stirring and can play a role of cleaning simultaneously in the prefabricated slurry tank and the water-coal-slurry tank, when preparing the water-coal-slurry, the waste slurry ground by a grinder is added into the tank body from the slurry inlet at the top of the tank body, the driven bevel gear is driven to rotate by the driving bevel gear connected with the driving motor, so as to drive the stirring shaft to rotate, the slurry in the tank body is fully stirred by the stirring paddle at the bottom of the stirring shaft, and the water-coal-slurry which is prepared after stirring is discharged from the slurry outlet at the bottom of the tank body and enters a subsequent device.

Meanwhile, the hollow and communicated stirring shaft and stirring paddle are adopted, and the stirring paddle is provided with a plurality of spraying ports, so that when the tank body is cleaned after pulping, high-pressure water flow can be introduced from a water inlet pipe sleeved in the stirring shaft from the upper part, the water flow is sprayed out from the spraying ports on the stirring paddle, the interior of the tank body and the stirring paddle are cleaned, and the cleaning operation is convenient; and the rotation of the stirring paddle can ensure that water flow is uniformly sprayed in the tank body, thereby improving the cleaning effect and ensuring that all parts in the tank body can be effectively cleaned.

Preferably, one end of the stirring paddle, which is close to the inner wall of the tank body, is provided with a side wall brush which is in contact with the inner wall of the tank body; the bottom of the end of the stirring shaft in the tank body is provided with a bottom brush which is contacted with the bottom of the tank body.

According to the invention, the side wall hairbrush is arranged at one end of the stirring paddle, the bottom hairbrush is arranged at the bottom of the stirring shaft, the side wall and the bottom of the tank body can be cleaned through the side wall hairbrush and the bottom hairbrush during cleaning, so that the residues of wastes on the side wall and the bottom of the tank body are avoided, the cleaning is cleaner and more thorough, and the cleaning efficiency is improved.

Preferably, the top of the tank body is provided with a support frame for placing a driving motor.

The invention also provides a method for carrying out gasification cooperative treatment on the rectified high-boiling residue and the electroplating wastewater by using the system, which comprises the following steps:

(1) crushing raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal by sieves with different sizes to obtain coal powder with different particle sizes, and mixing the coal powder with different particle sizes to obtain graded coal powder; the rectified high-boiling residue, the activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated high-boiling residue powder, activated carbon powder and electroplating wastewater;

(2) feeding the pretreated high-boiling residue powder, the activated carbon powder and the electroplating wastewater into a pre-pulping unit together for primary grinding and stirring to obtain pre-pulping, wherein the primary grinding time is 10-20 min, and the primary stirring time is 5-20 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with graded coal powder and then is subjected to secondary grinding and stirring to obtain coal water slurry, wherein the secondary grinding time is 20-30 min, and the secondary stirring time is 5-20 min;

(4) and feeding the coal water slurry into a gasification furnace in the gasification treatment unit for combustion.

Preferably, the raw coal in the step (1) is crushed in a pretreatment unit and then respectively sieved by a 40-60 mesh sieve and a 80-100 mesh sieve, and the mass ratio of the raw coal to the raw coal is 1: (3-4) mixing to obtain the graded coal powder.

Preferably, the rectified high-boiling-point substance in the step (2) is crushed in a pretreatment unit and then sieved by a 60-80-mesh sieve to obtain high-boiling-point substance powder.

The invention mixes the coal powder with different grain diameters to obtain the graded coal powder, and crushes the rectified high-boiling-point substance into the high-boiling-point substance powder with different grain diameters from the coal powder, after the powders with different grain diameters are mixed, the high-boiling-point substance powder and the coal powder can jointly form the graded effect, the powder with small grain diameter can be filled among the large-grain powder, the gaps among the grains are reduced, the higher stacking efficiency is achieved, and the stability of the coal water slurry is improved.

Preferably, water and an additive are added in the step (2) and the step (3), and the coal water slurry obtained in the step (3) comprises 70-75 parts of graded coal powder, 15-20 parts of high-boiling-point substance powder, 5-8 parts of activated carbon powder, 25-35 parts of electroplating water, 35-45 parts of water and 1-2 parts of an additive in parts by weight.

Preferably, the activated carbon powder in the step (2) is surface modified activated carbon powder, and the preparation method comprises the following steps:

A) adding activated carbon into a nitric acid solution with the mass concentration of 20-50%, wherein the mass volume ratio of the activated carbon to the nitric acid is 1g (20-50 mL), reacting for 2-4 h at 80-90 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 90-110 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding proportion of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g (20-30 mL) to 1-3 g, reacting for 8-10 h under heat preservation, and filtering and washing a product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding proportion of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g (20-30 mL) to (3-5 mL), stirring and reacting for 10-15 h at 60-70 ℃ under the protection of nitrogen, and filtering and washing a product to obtain amino modified activated carbon;

D) adding amino modified activated carbon into ethanol and water in a volume ratio of (3-5): 1, adding chloroacetic acid and sodium bicarbonate into the mixed solvent of 1, wherein the addition ratio of the amino modified activated carbon to the mixed solvent to the chloroacetic acid to the sodium bicarbonate is (1 g, 30-50 mL) to (1-2 g): (1-1.5 g), stirring and reacting for 8-10 h at 55-65 ℃, filtering, washing, drying, grinding and sieving with a 400-600 mesh sieve to obtain the surface modified activated carbon powder.

Because the electroplating wastewater used in the invention contains more metal ions, and the metal ions can compress the double electric layers on the surfaces of the coal powder and the rectified high-boiling-point substance powder, so that the electrostatic repulsion among the solid powder is weakened, the solid powder is easy to agglomerate, and the stability of the coal water slurry is influenced, therefore, the active carbon is used for adsorbing the metal ions in the electroplating wastewater. However, since the surface of the activated carbon is hydrophobic and the metal ions are solvated in water, the affinity between the activated carbon and the metal ions is not strong, and the removal rate of the metal ions in the electroplating wastewater is not good by using the unmodified activated carbon.

Therefore, the surface of the activated carbon is modified, firstly, the gamma-chloropropyltrimethoxysilane is used for grafting triethylene tetramine on the surface of the activated carbon, chelating functional group amino capable of coordinating metal ions is introduced on the surface of the activated carbon, and through the step D), secondary amine in the triethylene tetramine is used for reacting with chloroacetic acid, carboxyl is further introduced, so that the surface of the activated carbon has various chelating functional groups, the chelating performance of the activated carbon on the metal ions is improved, the activated carbon can be chelated with various metal ions in the electroplating wastewater to form a stable structure, the removal effect of the metal ions is greatly improved, and the dispersibility and the stability of the prepared water-coal-slurry are improved; and the adsorption performance of the surface of the activated carbon is not influenced, and the activated carbon can effectively play roles in deodorizing and removing volatile organic compounds.

Preferably, the preparation method of the additive comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate into deionized water, and stirring for 30-40 min to obtain a mixed solution; heating to 75-85 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, and carrying out heat preservation reaction for 3-4 hours; adding 4-vinylpyridine, dropwise adding an ammonium persulfate solution for the second time, and continuously stirring for reacting for 1-2 h; cooling to below 50 ℃, and adjusting the pH to 6-7 by using a sodium hydroxide solution to obtain the additive; wherein the mol ratio of allyl polyoxyethylene ether, acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4-vinylpyridine is 1: (1.5-2): (0.4-0.6): (0.1 to 0.3); the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 35-45% of the mass of the mixed solution; the mass of ammonium persulfate in the ammonium persulfate solution dropwise added for the first time is 8-10% of that of the mixed solution, and the mass ratio of the ammonium persulfate solution dropwise added for the second time to the ammonium persulfate solution dropwise added for the first time is 1: (2-4).

The coal powder, the high-boiling-point substance powder, especially the activated carbon powder, have small particle size and large specific surface area, so that the powder is easy to agglomerate and settle after being prepared into the water-coal-slurry, and the dispersion stability of the water-coal-slurry is influenced. After the additive prepared by the invention is added into the coal water slurry, the additive can be adsorbed on the surfaces of coal particles and high-boiling-point substance powder through a hydrophobic main chain, and the electrostatic repulsion among the coal particles can be enhanced by hydrophilic groups such as carboxylic acid groups, sulfonic acid groups and the like, so that the agglomeration among the coal particles is avoided; the ether bond on the side chain can provide steric hindrance effect, and forms hydrogen bond with water molecule to form hydrophilic stereo film, thus improving the dispersion stability of the solid powder. Meanwhile, pyridine groups on the molecular chain of the additive can form a hydrogen bond action with carboxyl in the surface molecular chain of the activated carbon after surface modification, so that activated carbon powder filled between the coal powder and the high-boiling-point substance powder and the coal powder and the high-boiling-point substance powder are mutually crosslinked, and a space structure formed by mutually crosslinking powder particles can generate mechanical resistance to the precipitation of the solid powder and the activated carbon powder, thereby effectively preventing the precipitation of the activated carbon powder, further improving the dispersion stability of the system, and the prepared water-coal-slurry has good solid content, dispersibility, stability and combustion efficiency.

When the additive is prepared, monomers are added in a segmented mode, the addition amount of each monomer is controlled, firstly, allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate monomers are polymerized for a period of time, and the main functional segments of the polycarboxylic additive are distributed in the middle segment of a molecular chain; then adding 4-vinylpyridine monomer to participate in polymerization, so that two ends of the molecular chain can effectively form hydrogen bonds with the molecular chain on the surface of the active carbon, thereby forming a space structure, and simultaneously avoiding the chain segments in the additive from being excessively hybridized so as to weaken the dispersing performance of the additive.

Therefore, the invention has the following beneficial effects:

(1) the rectified high-boiling-point substances, the activated carbon, the electroplating wastewater and the coal powder are compatible, the compatibility and the synergistic effect among the wastes are fully utilized, the wastes and the coal powder are modified to prepare the high-performance coal water slurry, and the resource utilization and the harmless treatment of the wastes are realized by matching the wastes with the wastes prepared from wastes;

(2) the stirring and cleaning devices which can play a role in stirring and can also play a role in cleaning are arranged in the pre-slurry tank and the water-coal-slurry tank, so that the pre-slurry tank and the water-coal-slurry tank are convenient to clean, the cleaning effect and the cleaning efficiency are improved, and the influence of the residue of wastes in the tank body on the performance of the prepared water-coal-slurry is avoided, thereby influencing the treatment effect of the wastes;

(3) the surface of the activated carbon is modified, so that the surface of the activated carbon has various chelating functional groups, the chelating performance of the activated carbon on metal ions is improved, the removal effect of the metal ions is improved, the dispersibility and the stability of the prepared coal water slurry are improved, and the adsorption performance of the surface of the activated carbon is not influenced;

(4) and adding a polycarboxylic acid additive with a side chain having a pyridine group, wherein the pyridine group can form a hydrogen bond with carboxyl in a surface molecular chain of the activated carbon after surface modification, so that the activated carbon powder filled among the coal powder particles is crosslinked with the coal powder particles, and the formed space structure can further improve the dispersion stability of the system.

Drawings

Fig. 1 is a schematic diagram of the connection structure of the system of the present invention.

FIG. 2 is a schematic diagram of the construction of a pre-slurry tank and a coal-water slurry tank in the present invention.

In the figure: 1 raw material coal pretreatment unit, 101 storage bin, 102 crushing device, 103 screening device, 2 rectification high-boiling-point substance pretreatment unit, 3 active carbon pretreatment unit, 301 iron remover, 4 electroplating wastewater storage tank, 5 first mill, 6 prefabricated slurry tank, 601 tank body, 602 slurry inlet, 603 slurry outlet, 604 support frame, 7 second mill, 8 water coal slurry tank, 9 gasification furnace, 10 first water storage tank, 11 first additive storage tank, 12 second water storage tank, 13 second additive storage tank, 14 lift pump, 15 stirring shaft, 16 stirring paddle, 17 spray nozzle, 18 water inlet pipe, 19 driving motor, 20 driving bevel gear, 21 driven bevel gear, 22 side wall brush, 23 bottom brush.

Detailed Description

The invention is further described with reference to the following detailed description and accompanying drawings.

In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified. The raw material coal used in the embodiment of the invention is Shenmu coal; the rectification high-boiling-point substance is a rectification high-boiling-point substance produced by producing medicinal polyacrylic resin by Shandong Lu anti-medicine GmbH.

As shown in figure 1, the gasification co-processing system for the rectified high-boiling residue and the electroplating wastewater comprises a pretreatment unit, a pre-slurry unit, a coal water slurry synthesis unit and a gasification processing unit.

The pretreatment unit comprises a raw material coal pretreatment unit 1, a rectification high-boiling residue pretreatment unit 2, an electroplating wastewater pretreatment unit and an active carbon pretreatment unit 3 which are operated independently. The raw material coal pretreatment unit and the rectification high-boiling residue pretreatment unit respectively comprise a storage bin 101, a crushing device 102 and a screening device 103 which are connected in sequence; the activated carbon pretreatment unit comprises a storage bin, an iron remover 301 and a screening device which are connected in sequence; the electroplating wastewater pretreatment unit includes an electroplating wastewater tank 4.

The pre-slurry unit comprises a first mill 5, a pre-slurry tank 6, a first water storage tank 10 and a first additive storage tank 11; the first mill adopts a rod mill, a feed inlet of the rod mill is respectively connected with a screening device, an electroplating wastewater storage tank, a first water storage tank and a first additive storage tank in the rectification high-boiling-point substance pretreatment unit and the active carbon pretreatment unit, and a discharge outlet of the rod mill is connected with the pre-prepared slurry tank.

The coal water slurry synthesis unit comprises a second mill 7, a coal water slurry tank 8, a second water storage tank 12 and a second additive storage tank 13; the second mill adopts a ball mill, a feed inlet of the ball mill is respectively connected with a screening device, a prefabricated slurry tank, a second water storage tank and a second additive storage tank in the raw material coal pretreatment unit, and a discharge outlet of the ball mill is connected with a water-coal slurry tank. The gasification treatment unit comprises a gasification furnace 9 connected with a water-coal slurry tank, and a lifting pump 14 is arranged on a pipeline between the water-coal slurry tank and the gasification furnace.

As shown in fig. 2, the pre-slurry tank and the coal-water slurry tank include a tank body 601 and a stirring and cleaning device disposed in the tank body, a slurry inlet 602 and a support frame 604 are disposed at the top of the tank body, and a slurry outlet 603 is disposed at the bottom of the tank body; stirring belt cleaning device includes that one end is connected with the drive arrangement who sets up at jar body top, the other end stretches into the (mixing) shaft 15 of jar internal bottom, and set up six stirring rakes 16 that are located jar internal one end at the (mixing) shaft, (mixing) shaft and stirring rake cavity are linked together, stirring rake outer wall downside is equipped with a plurality of edge stirring rake length direction evenly distributed's mouth 17 that sprays, the one end that the stirring rake is close to jar internal wall is equipped with the lateral wall brush 22 with jar internal wall contact, the (mixing) shaft is located jar internal one end bottom be equipped with jar bottom contact's bottom brush 23, the one end endotheca that the (mixing) shaft. The driving device comprises a driving motor 19 arranged on the supporting frame, a driving bevel gear 20 connected with the driving motor and a driven bevel gear 21 in transmission connection with the driving bevel gear, and the driven bevel gear is in transmission connection with the stirring shaft.

Example 1:

(1) crushing the raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal with 40-mesh and 80-mesh sieves, and mixing the crushed raw material coal with the raw material coal according to a mass ratio of 1: 3.5, mixing to obtain graded coal powder; crushing the rectified high-boiling-point substance in a pretreatment unit, and sieving the crushed rectified high-boiling-point substance with a 60-mesh sieve to obtain high-boiling-point substance powder; the activated carbon powder is subjected to iron removal in a pretreatment unit and then is sieved by a 500-mesh sieve, so that the pretreated activated carbon powder is obtained; the electroplating wastewater passes through a pretreatment unit to obtain pretreated electroplating wastewater;

(2) mixing 18 parts of high-boiling-point substance powder, 6 parts of activated carbon powder, 30 parts of electroplating wastewater, 10 parts of water and 0.5 part of additive in parts by weight in a pre-pulping unit, and performing rod milling and stirring once to obtain pre-pulping, wherein the rod milling time is 15min, the primary stirring speed is 500rpm, and the stirring time is 10 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 71 parts of coal powder, 30 parts of water and 1 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 25min, the secondary stirring speed is 500rpm, and the stirring time is 10 min; the additive adopts a naphthalene dispersant produced by Huainan chemical plants;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0 MPa.

Example 2:

(1) crushing the raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal with 40-mesh and 80-mesh sieves, and mixing the crushed raw material coal with the raw material coal according to a mass ratio of 1: 3.5, mixing to obtain graded coal powder; crushing the rectified high-boiling-point substance in a pretreatment unit, and sieving the crushed rectified high-boiling-point substance with a 60-mesh sieve to obtain high-boiling-point substance powder; the surface modified activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated surface modified activated carbon powder and electroplating wastewater;

the preparation method of the surface modified activated carbon powder comprises the following steps:

A) adding activated carbon powder into a nitric acid solution with the mass concentration of 30%, wherein the mass volume ratio of the activated carbon powder to the nitric acid is 1g:30mL, reacting for 3h at 85 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 100 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding ratio of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g to 25mL to 2g, reacting for 9 hours under heat preservation, and filtering and washing a product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding ratio of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g:25mL:4mL, stirring and reacting for 12h at 65 ℃ under the protection of nitrogen, and filtering and washing a product to obtain amino modified activated carbon;

D) adding amino modified activated carbon into ethanol and water in a volume ratio of 4: 1, adding chloroacetic acid and sodium bicarbonate into the mixed solvent of 1, wherein the addition ratio of the amino modified activated carbon to the mixed solvent to the chloroacetic acid to the sodium bicarbonate is 1g:40mL:1.5g:12g, stirring and reacting for 9h at 60 ℃, filtering, washing, drying and grinding the product, and then sieving with a 500-mesh sieve to obtain surface modified activated carbon powder;

(2) mixing 18 parts of high-boiling-point substance powder, 6 parts of activated carbon powder, 30 parts of electroplating wastewater, 10 parts of water and 0.5 part of additive in parts by weight in a pre-pulping unit, and performing rod milling and stirring once to obtain pre-pulping, wherein the rod milling time is 15min, the primary stirring speed is 500rpm, and the stirring time is 10 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 71 parts of coal powder, 30 parts of water and 1 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 25min, the secondary stirring speed is 500rpm, and the stirring time is 10 min; the additive adopts a naphthalene dispersant produced by Huainan chemical plants;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0 MPa.

Example 3:

(1) crushing the raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal with 40-mesh and 80-mesh sieves, and mixing the crushed raw material coal with the raw material coal according to a mass ratio of 1: 3.5, mixing to obtain graded coal powder; crushing the rectified high-boiling-point substance in a pretreatment unit, and sieving the crushed rectified high-boiling-point substance with a 60-mesh sieve to obtain high-boiling-point substance powder; the activated carbon powder is subjected to iron removal in a pretreatment unit and then is sieved by a 500-mesh sieve, so that the pretreated activated carbon powder is obtained; the electroplating wastewater passes through a pretreatment unit to obtain pretreated electroplating wastewater;

(2) mixing 18 parts of high-boiling-point substance powder, 6 parts of activated carbon powder, 30 parts of electroplating wastewater, 10 parts of water and 0.5 part of additive in parts by weight in a pre-pulping unit, and performing rod milling and stirring once to obtain pre-pulping, wherein the rod milling time is 15min, the primary stirring speed is 500rpm, and the stirring time is 10 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 71 parts of coal powder, 30 parts of water and 1 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 25min, the secondary stirring speed is 500rpm, and the stirring time is 10 min;

the preparation method of the used additive comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate into deionized water, and stirring for 35min to obtain a mixed solution; heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, and carrying out heat preservation reaction for 3.5 hours; then adding 4-vinylpyridine and dropwise adding an ammonium persulfate solution for the second time, and continuously stirring for reaction for 1.5 h; cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive. Wherein the molecular weight of the allyl polyoxyethylene ether is 2000, and the mole ratio of the added allyl polyoxyethylene ether, the added acrylic acid, the added 2-acrylamide-2-sodium methylacrylsulfonate and the added 4-vinylpyridine is 1: 1.8: 0.5: 0.2; the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 40 percent of the mass of the mixed solution; the mass of the ammonium persulfate in the ammonium persulfate solution dripped for the first time is 9% of that of the mixed solution, and the mass ratio of the ammonium persulfate solution dripped for the second time to the ammonium persulfate solution dripped for the first time is 1: 3;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0 MPa.

Example 4:

(1) crushing the raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal with 40-mesh and 80-mesh sieves, and mixing the crushed raw material coal with the raw material coal according to a mass ratio of 1: 3.5, mixing to obtain graded coal powder; crushing the rectified high-boiling-point substance in a pretreatment unit, and sieving the crushed rectified high-boiling-point substance with a 60-mesh sieve to obtain high-boiling-point substance powder; the surface modified activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated surface modified activated carbon powder and electroplating wastewater;

the preparation method of the surface modified activated carbon powder comprises the following steps:

A) adding activated carbon powder into a nitric acid solution with the mass concentration of 30%, wherein the mass volume ratio of the activated carbon powder to the nitric acid is 1g:30mL, reacting for 3h at 85 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 100 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding ratio of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g to 25mL to 2g, reacting for 9 hours under heat preservation, and filtering and washing a product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding ratio of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g:25mL:4mL, stirring and reacting for 12h at 65 ℃ under the protection of nitrogen, and filtering and washing a product to obtain amino modified activated carbon;

D) adding amino modified activated carbon into ethanol and water in a volume ratio of 4: 1, adding chloroacetic acid and sodium bicarbonate into the mixed solvent of 1, wherein the addition ratio of the amino modified activated carbon to the mixed solvent to the chloroacetic acid to the sodium bicarbonate is 1g:40mL:1.5g:12g, stirring and reacting for 9h at 60 ℃, filtering, washing, drying and grinding the product, and then sieving with a 500-mesh sieve to obtain surface modified activated carbon powder;

(2) mixing 18 parts of high-boiling-point substance powder, 6 parts of activated carbon powder, 30 parts of electroplating wastewater, 10 parts of water and 0.5 part of additive in parts by weight in a pre-pulping unit, and performing rod milling and stirring once to obtain pre-pulping, wherein the rod milling time is 15min, the primary stirring speed is 500rpm, and the stirring time is 10 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 71 parts of coal powder, 30 parts of water and 1 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 25min, the secondary stirring speed is 500rpm, and the stirring time is 10 min;

the preparation method of the used additive comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate into deionized water, and stirring for 35min to obtain a mixed solution; heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, and carrying out heat preservation reaction for 3.5 hours; then adding 4-vinylpyridine and dropwise adding an ammonium persulfate solution for the second time, and continuously stirring for reaction for 1.5 h; cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive. Wherein the molecular weight of the allyl polyoxyethylene ether is 2000, and the mole ratio of the added allyl polyoxyethylene ether, the added acrylic acid, the added 2-acrylamide-2-sodium methylacrylsulfonate and the added 4-vinylpyridine is 1: 1.8: 0.5: 0.2; the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 40 percent of the mass of the mixed solution; the mass of the ammonium persulfate in the ammonium persulfate solution dripped for the first time is 9% of that of the mixed solution, and the mass ratio of the ammonium persulfate solution dripped for the second time to the ammonium persulfate solution dripped for the first time is 1: 3;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0 MPa.

Example 5:

(1) crushing the raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal with a 60-mesh sieve and a 100-mesh sieve, and mixing the crushed raw material coal with the raw material coal according to a mass ratio of 1: 3, mixing to obtain graded coal powder; crushing the rectified high-boiling-point substance in a pretreatment unit, and sieving the crushed rectified high-boiling-point substance with a 80-mesh sieve to obtain high-boiling-point substance powder; the surface modified activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated surface modified activated carbon powder and electroplating wastewater;

the preparation method of the surface modified activated carbon powder comprises the following steps:

A) adding activated carbon powder into a nitric acid solution with the mass concentration of 20%, wherein the mass volume ratio of the activated carbon powder to the nitric acid is 1g:50mL, reacting for 4 hours at 80 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 90 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding ratio of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g to 20mL to 1g, carrying out heat preservation reaction for 10h, and filtering and washing a product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding ratio of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g:20mL:3mL, stirring and reacting for 10 hours at 60 ℃ under the protection of nitrogen, and filtering and washing a product to obtain amino modified activated carbon;

D) adding amino modified activated carbon into ethanol and water in a volume ratio of 3: 1, adding chloroacetic acid and sodium bicarbonate into the mixed solvent of the mixed solvent, wherein the addition ratio of the amino modified activated carbon to the mixed solvent to the chloroacetic acid to the sodium bicarbonate is 1g:30mL:1g:1.5g, stirring and reacting for 10 hours at 55 ℃, filtering, washing, drying and grinding the product, and then sieving the product with a 600-mesh sieve to obtain surface modified activated carbon powder;

(2) mixing 15 parts of high-boiling-point substance powder, 5 parts of activated carbon powder, 25 parts of electroplating wastewater, 10 parts of water and 0.5 part of additive in parts by weight in a pre-pulping unit, and performing rod milling and stirring for 10min, 300rpm and 20min to obtain pre-pulping slurry;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 70 parts of coal powder, 25 parts of water and 0.5 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 30min, the secondary stirring speed is 300rpm, and the stirring time is 20 min;

the preparation method of the used additive comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate into deionized water, and stirring for 30min to obtain a mixed solution; heating to 75 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, and carrying out heat preservation reaction for 4 hours; adding 4-vinylpyridine, dropwise adding an ammonium persulfate solution for the second time, and continuously stirring for reacting for 1 h; cooling to below 50 ℃, and adjusting the pH to 6.1 by using a sodium hydroxide solution to obtain the additive. Wherein the molecular weight of the allyl polyoxyethylene ether is 1600, and the mole ratio of the added allyl polyoxyethylene ether, the added acrylic acid, the added 2-acrylamide-2-sodium methylacrylsulfonate and the added 4-vinylpyridine is 1: 1.5: 0.4: 0.1; the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 35 percent of the mass of the mixed solution; the mass of the ammonium persulfate in the ammonium persulfate solution dripped for the first time is 8% of that of the mixed solution, and the mass ratio of the ammonium persulfate solution dripped for the second time to the ammonium persulfate solution dripped for the first time is 1: 2;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 10s at the temperature of 1100 ℃ and the pressure of 4.0 MPa.

Example 6:

(1) crushing the raw material coal in a pretreatment unit, respectively sieving the crushed raw material coal with a 60-mesh sieve and a 100-mesh sieve, and mixing the crushed raw material coal with the raw material coal according to a mass ratio of 1: 4, mixing to obtain graded coal powder; crushing the rectified high-boiling-point substance in a pretreatment unit, and sieving the crushed rectified high-boiling-point substance with a 80-mesh sieve to obtain high-boiling-point substance powder; the surface modified activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated surface modified activated carbon powder and electroplating wastewater;

the preparation method of the surface modified activated carbon powder comprises the following steps:

A) adding activated carbon powder into a nitric acid solution with the mass concentration of 50%, wherein the mass volume ratio of the activated carbon powder to the nitric acid is 1g:20mL, reacting for 2h at 90 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 110 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding ratio of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g to 30mL to 3g, reacting for 8 hours under heat preservation, and filtering and washing the product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding ratio of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g:30mL:5mL, stirring and reacting for 15h at 70 ℃ under the protection of nitrogen, and filtering and washing a product to obtain amino modified activated carbon;

D) adding amino modified activated carbon into ethanol and water in a volume ratio of 5: 1, adding chloroacetic acid and sodium bicarbonate into the mixed solvent of 1, wherein the addition ratio of the amino modified activated carbon to the mixed solvent to the chloroacetic acid to the sodium bicarbonate is 1g:50mL:2g:1g, stirring and reacting at 65 ℃ for 8 hours, filtering, washing, drying and grinding the product, and then sieving with a 400-mesh sieve to obtain surface modified activated carbon powder;

(2) in a pre-pulping unit, mixing 20 parts of high-boiling-point substance powder, 8 parts of activated carbon powder, 35 parts of electroplating wastewater, 10 parts of water and 1 part of additive in parts by weight, and performing rod milling and stirring for 20min, 600rpm and 5min to obtain pre-pulping;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 75 parts of coal powder, 35 parts of water and 1 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 20min, the secondary stirring speed is 600rpm, and the stirring time is 5 min;

the preparation method of the used additive comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate into deionized water, and stirring for 40min to obtain a mixed solution; heating to 85 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, and carrying out heat preservation reaction for 3 hours; then adding 4-vinylpyridine, dropwise adding an ammonium persulfate solution for the second time, and continuously stirring for reaction for 2 hours; cooling to below 50 ℃, and adjusting the pH to 6.9 by using a sodium hydroxide solution to obtain the additive. Wherein the molecular weight of the allyl polyoxyethylene ether is 2400, and the molar ratio of the added allyl polyoxyethylene ether, the added acrylic acid, the added 2-acrylamide-2-sodium methylacrylsulfonate and the added 4-vinylpyridine is 1: 2: 0.6: 0.3; the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 45 percent of the mass of the mixed solution; the mass of the ammonium persulfate in the ammonium persulfate solution dripped for the first time is 10% of that of the mixed solution, and the mass ratio of the ammonium persulfate solution dripped for the second time to the ammonium persulfate solution dripped for the first time is 1: 4;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 6s at the temperature of 1500 ℃ and the pressure of 0.8 MPa.

Comparative example 1:

(1) crushing the raw material coal and the rectified high-boiling residue in a pretreatment unit, and then sieving the crushed raw material coal and the rectified high-boiling residue by a 40-mesh sieve to obtain coal powder and high-boiling residue powder; the surface modified activated carbon powder and the electroplating wastewater are pretreated by a pretreatment unit to obtain pretreated surface modified activated carbon powder and electroplating wastewater; the preparation method of the surface modified activated carbon is the same as that in example 4;

(2) mixing 18 parts of high-boiling-point substance powder, 6 parts of activated carbon powder, 30 parts of electroplating wastewater, 10 parts of water and 0.5 part of additive in parts by weight in a pre-pulping unit, and performing rod milling and stirring once to obtain pre-pulping, wherein the rod milling time is 15min, the primary stirring speed is 500rpm, and the stirring time is 10 min;

(3) the pre-slurrying enters a coal water slurry synthesis unit, is mixed with 71 parts of coal powder, 30 parts of water and 1 part of additive, and then is subjected to secondary ball milling and stirring to obtain coal water slurry, wherein the ball milling time is 25min, the secondary stirring speed is 500rpm, and the stirring time is 10 min; the preparation method of the additive is the same as that in example 4;

(4) feeding the coal water slurry into a gasification furnace in a gasification treatment unit, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0 MPa.

Comparative example 2:

the preparation method of the surface-modified activated carbon used in comparative example 2 was:

A) adding activated carbon powder into a nitric acid solution with the mass concentration of 30%, wherein the mass volume ratio of the activated carbon powder to the nitric acid is 1g:30mL, reacting for 3h at 85 ℃, filtering and washing a product to obtain activated carbon;

B) adding activated carbon into toluene, heating to 100 ℃ under a stirring state, adding gamma-chloropropyl trimethoxy silane, wherein the adding ratio of the activated carbon to the toluene to the gamma-chloropropyl trimethoxy silane is 1g to 25mL to 2g, reacting for 9 hours under heat preservation, and filtering and washing a product to obtain silane modified activated carbon;

C) adding silane modified activated carbon into absolute ethyl alcohol, adding triethylene tetramine, wherein the adding ratio of the silane modified activated carbon to the absolute ethyl alcohol to the triethylene tetramine is 1g:25mL:4mL, stirring and reacting for 12h at 65 ℃ under the protection of nitrogen, filtering, washing, drying and grinding the product, and then sieving with a 500-mesh sieve to obtain the surface modified activated carbon powder.

The rest is the same as in example 4.

Comparative example 3:

the preparation method of the additive used in comparative example 3 was: sequentially adding allyl polyoxyethylene ether, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate into deionized water, and stirring for 35min to obtain a mixed solution; and (3) heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, keeping the temperature, reacting for 5 hours, cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive. Wherein the molecular weight of the allyl polyoxyethylene ether is 2000, and the molar ratio of the added allyl polyoxyethylene ether, the added acrylic acid and the added 2-acrylamide-2-sodium methylacrylsulfonate is 1: 1.8: 0.5; the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 40 percent of the mass of the mixed solution; the mass of the ammonium persulfate in the dropwise added ammonium persulfate solution is 12% of that of the mixed solution.

The rest is the same as in example 4.

Comparative example 4:

the preparation method of the additive used in comparative example 4 was: sequentially adding allyl polyoxyethylene ether, acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4-vinylpyridine into deionized water, and stirring for 35min to obtain a mixed solution; heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, and carrying out heat preservation reaction for 5 hours; cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive. Wherein the molecular weight of the allyl polyoxyethylene ether is 2000, and the mole ratio of the added allyl polyoxyethylene ether, the added acrylic acid, the added 2-acrylamide-2-sodium methylacrylsulfonate and the added 4-vinylpyridine is 1: 1.8: 0.5: 0.2; the total mass of the allyl polyoxyethylene ether, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and the 4-vinylpyridine accounts for 40 percent of the mass of the mixed solution; the mass of the ammonium persulfate in the dropwise added ammonium persulfate solution is 12% of that of the mixed solution.

The rest is the same as in example 4.

The performance indexes of the coal water slurries prepared in the above examples and comparative examples and the content of effective gas in the synthesis gas obtained after combustion were tested, and the results are shown in table 1.

Wherein it is contained inMeasuring by using a quick water meter, namely weighing about 2g of sample, drying for 30 minutes at 105 ℃, and obtaining the solid content by the residual weight; the apparent viscosity of the slurry was measured using a Brookfield R/S-CC + type rheometer (C40 rotor) at a shear rate of 100S^-1Viscosity at room temperature.

The fluidity and stability (24-hour stability) of the slurry were observed and graded as A⁺、A、A^-、B⁺、B、B^-、C⁺、C、C^-、D⁺、D、D^-12 stages in total; fluidity from A⁺～D^-In the order of decreasing, A⁺For rapid continuous flow, D^-Is completely non-flowing; stability from A⁺～D^-In the order of decreasing, A⁺To avoid precipitation and precipitation, D^-To produce a hard precipitate and cannot be restored to the original state by stirring the slurry.

Table 1: and (5) testing the performance of the coal water slurry.

Numbering	Solid content (%)	Apparent viscosity (mPa. s)	Flow rating	Grade of stability	Effective gas content (%)
						Example 1	57.32	856	C	C+	74.2
Example 2	58.88	821	C	B-	76.1
						Example 3	59.97	541	A-	B	77.0
Example 4	61.13	562	A-	A+	79.8
						Example 5	60.48	537	A-	A	79.2
Example 6	61.05	655	B+	A-	79.5
						Comparative example 1	57.16	516	A-	C-	74.0
Comparative example 2	59.06	527	A-	B+	76.6
						Comparative example 3	58.91	535	A-	B+	76.3
Comparative example 4	58.35	768	B	C	75.7

As can be seen from Table 1, the solid content of the coal water slurry obtained by using the system of the present invention in example 1 is high, and the content of the effective gas after combustion is also high, but the fluidity and stability of the coal water slurry are not very ideal by using the commercial naphthalene catalyst; in the embodiment 2, the activated carbon with the modified surface is adopted, so that the stability of the coal water slurry is improved; but the flowability is still poor; in the embodiment 3, the polycarboxylic acid additive prepared by the invention is adopted, so that the fluidity of the coal water slurry is obviously improved, but the stability is insufficient; in the embodiments 4 to 6, the surface modified activated carbon prepared by the method of the present invention and the additive are simultaneously added, and the high performance coal water slurry with high solid content and good fluidity and stability is obtained under the synergistic effect of the components.

In the comparative example 1, the coal powder and the high-boiling-point substance powder have the same particle size, and grading is not performed, so that the dispersibility and the stability of the prepared coal water slurry are reduced compared with those of the coal water slurry prepared in the example 4, and the coal powder and the high-boiling-point substance powder are graded to effectively improve various properties of the coal water slurry; in the comparative example 2, no carboxyl is introduced when the surface modification is carried out on the activated carbon, the stability of the coal water slurry is reduced compared with that of the example 4, probably because the chelation performance of the carboxyl-based activated carbon to metal ions is reduced without introducing the carboxyl-based activated carbon, and the carboxyl-based activated carbon cannot act with an additive, so that the activated carbon and coal particles are mutually crosslinked to form a spatial structure; compared with the additive in the comparative example 3, no pyridine group is introduced, so that the stability of the coal water slurry is reduced, and the active carbon and the coal particles are mutually crosslinked to form a space structure, so that the stability of the coal water slurry can be effectively improved; and in the comparative example 4, each monomer is added simultaneously when the additive is prepared, so that the fluidity and the stability of the coal water slurry are obviously reduced, and the addition mode of the monomer has great influence on the dispersibility of the additive.

The results of analyzing the trace elements in the synthesis gas obtained after the combustion of the coal water slurries of examples 4 to 6 are shown in table 2.

Table 2: and analyzing the trace elements of the synthesis gas.

As can be seen from Table 2, the characteristic pollutants of sulfur, chlorine, fluorine and nitrogen in the combustion process of the coal water slurry prepared by the method are far lower than the emission standard; volatile heavy metal pollutants are not easy to enter the synthesis gas and are far lower than the emission standard; the emission value of dioxin substances in high-temperature reducing atmosphere is far lower than the emission standard. The coal water slurry prepared from the rectified high-boiling residues and the electroplating wastewater can realize resource utilization and clean treatment of wastes.