CN214694314U

CN214694314U - Equipment for recovering titanium and simultaneously extracting ammonium chloride from olefin polymerization industrial waste acid residues

Info

Publication number: CN214694314U
Application number: CN202023148280.0U
Authority: CN
Inventors: 汤豪; 张艳芬; 于连杰; 胡海龙
Original assignee: Beijing Yanshan Xiangyu Environmental Protection Engineering Tech Co ltd; China Petroleum and Chemical Corp; Sinopec Catalyst Co
Current assignee: Beijing Yanshan Xiangyu Environmental Protection Engineering Tech Co ltd; China Petroleum and Chemical Corp; Sinopec Catalyst Co
Priority date: 2020-12-24
Filing date: 2020-12-24
Publication date: 2021-11-12
Anticipated expiration: 2030-12-24

Abstract

The utility model discloses an equipment of retrieving titanium and drawing ammonium chloride simultaneously in follow olefin polymerization industry waste acid sludge, this equipment include normal atmospheric temperature normal pressure system of hydrolysising, ozone catalytic oxidation system, middle filtration system, aqueous ammonia and add magnesium dephosphorization desiliconization system, tubular micro-filtration membrane system, multiple effect evaporation concentration system, hydrochloric acid neutralization system, electrodialysis membrane concentration system, evaporative crystallization system. The utility model discloses can follow olefin polymerization industry waste acid sludge and retrieve titanium in a large number, the by-product ammonium chloride chemical fertilizer that technology operation requires lowly, the rate of recovery is high, produce simultaneously, friendly to the environment, have wide industrial application prospect.

Description

Equipment for recovering titanium and simultaneously extracting ammonium chloride from olefin polymerization industrial waste acid residues

Technical Field

The utility model belongs to the technical field of petrochemical, especially, relate to the recovery of titanium tetrachloride in the industrial production of olefin polymerization catalyst, specifically be an equipment that retrieves titanium and draws ammonium chloride simultaneously in follow olefin polymerization industry waste acid sludge.

Background

Titanium tetrachloride is an important and largely used raw material in the industrial production of olefin polymerization catalysts, and a large amount of titanium tetrachloride-containing acid sludge is produced after use. The water quality components of the waste acid sludge are very complicated. However, the cation is mainly titanium, accounting for about 99%, and the anion is only chlorine.

There are two prior art methods for treating waste acid sludge. The first method is to add the acid sludge into the quicklime for neutralization reaction to produce a large amount of precipitate, and then separate the precipitate by using a plate-and-frame filter press. Valuable titanium cannot be recovered by plate and frame filter pressing. The second method is to directly adopt a high-temperature evaporation process to the waste acid residues to evaporate hydrochloric acid in the waste acid residues, titanium oxide crystals can be generated at the bottom of an evaporation kettle, but the requirement on corrosion resistance of equipment is extremely high due to the fact that the evaporation kettle works in a hydrochloric acid environment, and batch production and long-period operation are difficult to achieve. Moreover, the second method has the following problems: the bottom temperature of the distillation tower is high, which causes the alkoxy titanium and the ester titanium complexDecomposition, coking and fouling of organic compounds such as compounds, and the evaporation temperature needs to be controlled to leave a certain amount of TiCl for easy discharge of the bottom₄. Thus greatly reducing TiCl₄The recovery rate is increased, and the amount of waste is increased. And a large amount of acid water, acid gas and waste residues are generated when the waste is reprocessed, so that the waste is not easy to treat and pollutes the environment.

Disclosure of Invention

An object of the utility model is to overcome prior art's defect, provide one kind and can follow and draw high-purity titanium liquid in the olefin polymerization industry acid sludge, can make the process energy-concerving and environment-protective of purification titanium liquid again, with the equipment of its accessory substance resourceful treatment.

The purpose of the utility model is realized like this:

an apparatus for recovering titanium and simultaneously extracting ammonium chloride from waste acid residues in olefin polymerization industry comprises a normal temperature and normal pressure hydrolysis system, an ozone catalytic oxidation system, an intermediate filtration system, an ammonia water neutralization, dephosphorization, desiliconization and magnesium addition system, a tubular microfiltration membrane system, a multi-effect evaporation concentration system, a hydrochloric acid neutralization system, an electrodialysis membrane concentration system and an evaporation crystallization system; the normal temperature and normal pressure hydrolysis system comprises a primary hydrolysis system and a secondary hydrolysis system; the liquid outlet end of the hydrolysate of the normal-temperature normal-pressure hydrolysis system is connected to the liquid inlet end of the ozone catalytic oxidation system through a water pump and a hydrolysis supernatant liquid output pipeline; the liquid outlet end of the ozone catalytic oxidation system is connected to the liquid inlet end of the intermediate filtering system through a pipeline; the liquid outlet end of the intermediate filtering system is connected to the liquid inlet end of the ammonia water neutralization and magnesium addition phosphorus and silicon removal system through a pipeline; the liquid outlet end of the ammonia water neutralization and magnesium addition dephosphorization and desilication system is connected to the titanium hydroxide liquid inlet end of the tubular microfiltration membrane system through a pipeline; the titanium hydroxide liquid outlet end of the tubular microfiltration membrane system is connected to a material liquid inlet of the multi-effect evaporation concentration system through a pipeline; the membrane produced water outlet end of the tubular microfiltration membrane system is connected to the liquid inlet end of the hydrochloric acid neutralization system through a pipeline, and the evaporation condensate outlet of the multi-effect evaporation concentration system is connected to the liquid inlet end of the hydrochloric acid neutralization system through a pipeline; the liquid outlet end of the hydrochloric acid neutralization system is connected with the liquid inlet end of the electrodialysis membrane concentration system through a pipeline; the concentrated solution outlet end of the electrodialysis membrane concentration system is connected with the evaporative crystallization system through a pipeline.

According to a further optimization scheme, the normal-temperature and normal-pressure hydrolysis system comprises a primary hydrolysis system, a secondary hydrolysis system, a waste acid residue collecting system, a filter pressing system, a hydrolysis supernatant collecting device, a clear water inlet pipe and a waste acid residue feeding device; the primary hydrolysis system comprises: a primary hydrolysis tank, a primary hydrolysis circulating pump and a primary hydrolysis output pump; the secondary hydrolysis system comprises: a secondary hydrolysis tank, a secondary hydrolysis circulating pump and a secondary hydrolysis output pump; the waste acid sludge collecting system comprises: a sludge tank and a sludge feed pump; the primary hydrolysis tank and the secondary hydrolysis tank are respectively provided with a waste acid residue inlet, a waste acid residue and circulating water outlet, a liquid inlet, a hydrolysis supernatant outlet and a circulating water inlet; a waste acid residue inlet of the primary hydrolysis tank is connected with the waste acid residue feeding device; the liquid inlet of the first-stage hydrolysis tank is connected to the clear water inlet pipe through a branch pipeline, and a water inlet valve of the first-stage hydrolysis tank is arranged on the branch pipeline; the waste acid sludge and circulating water outlet of the first-stage hydrolysis tank is connected to the water inlet end of the first-stage hydrolysis circulating pump through a pipeline, the water outlet end pipeline of the first-stage hydrolysis circulating pump is divided into two branch pipelines which are respectively connected to the circulating water inlet of the first-stage hydrolysis tank and the waste acid sludge inlet of the second-stage hydrolysis tank, wherein the branch pipeline connected with the circulating water inlet of the first-stage hydrolysis tank is provided with a first-stage hydrolysis tank inlet circulating valve, and the branch pipeline connected with the waste acid sludge inlet of the second-stage hydrolysis tank is provided with a first-stage hydrolysis tank outlet discharge valve; a supernatant outlet of the primary hydrolysis tank is connected to a water inlet end of the primary hydrolysis outward-conveying pump, and a water outlet pipeline of the primary hydrolysis outward-conveying pump is connected to a hydrolysis supernatant collecting device; the liquid inlet of the secondary hydrolysis tank is connected to the clear water inlet pipe through a branch pipeline, and a water inlet valve of the secondary hydrolysis tank is arranged on the branch pipeline; the waste acid sludge and circulating water outlet of the second-stage hydrolysis tank is connected to the water inlet end of a second-stage hydrolysis circulating pump through a pipeline, the water outlet end pipeline of the second-stage hydrolysis circulating pump is divided into two branch pipelines which are respectively connected to the circulating water inlet of the second-stage hydrolysis tank and the inlet of the sludge tank, wherein a second-stage hydrolysis tank inlet circulating valve is arranged on the branch pipeline connected with the circulating water inlet of the second-stage hydrolysis tank, and a second-stage hydrolysis tank outlet discharge valve is arranged on the branch pipeline connected with the inlet of the sludge tank; a supernatant outlet of the secondary hydrolysis tank is connected to a water inlet end of the secondary hydrolysis outward-conveying pump, and a water outlet pipeline of the secondary hydrolysis outward-conveying pump is connected to a hydrolysis supernatant collecting device; the export of sludge case passes through the feed end of tube coupling mud feed pump, and the discharge end of mud feed pump passes through tube coupling to filter-pressing system, and filter-pressing system's filtrating discharge line inserts the second grade case of hydrolysising.

Further, the ozone catalytic oxidation system comprises an ozone reaction tower, an ozone generator, an ozone destructor and an oxidation water production tank; the top of the ozone reaction tower is provided with an ozone destructor, the inside of the ozone reaction tower is provided with an upper layer of clapboard with holes and a lower layer of clapboard with holes, a catalyst packing layer is arranged between the two layers of clapboards, the bottom of the ozone reaction tower is fixed with an air duct, the air duct is provided with a plurality of micron bubble aeration heads, and an air inlet interface of the air duct is connected with an air duct of the ozone generator; a hydrolysis supernatant inlet is arranged on the side wall of the ozone reaction tower and positioned below the catalyst packing layer, and the hydrolysis supernatant inlet is connected to a hydrolysis liquid outlet end of the normal-temperature normal-pressure hydrolysis system through a pipeline; a water outlet after reaction is arranged on the side wall of the ozone reaction tower above the catalyst packing layer and is connected with a water inlet of the oxidation water production tank through a pipeline; the middle filtering system comprises a filter and a filter water feeding pump connected with the filter, a water outlet of the oxidation product water tank is connected with a water inlet end of the filter water feeding pump through a pipeline, a water outlet end of the filter water feeding pump is connected with a water inlet end of the filter, and a water outlet end of the filter is connected with the ammonia water neutralizing and magnesium adding phosphorus and silicon removing system; the ammonia water neutralization and magnesium-adding phosphorus and silicon removal system comprises an ammonia water neutralization tank, a phosphorus and silicon removal tank, a neutralization sludge discharge pump, an ammonia water feeding device and a magnesium agent feeding device, wherein the phosphorus and silicon removal tank is communicated with the ammonia water neutralization tank, the bottom of the phosphorus and silicon removal tank is conical, a water inlet of the ammonia water neutralization tank is connected with a water outlet end of the filter, the ammonia water neutralization tank is connected with the phosphorus and silicon removal tank through an overflow port, the bottom of the phosphorus and silicon removal tank is provided with a precipitation outlet and is connected to the neutralization sludge discharge pump through a pipeline, the side wall of the phosphorus and silicon removal tank is provided with a titanium hydroxide suspension overflow port, and the titanium hydroxide suspension overflow port is connected to the tubular microfiltration membrane system; the ammonia water adding device comprises an ammonia water storage tank and an ammonia water dosing pump, wherein the liquid outlet end of the ammonia water storage tank is connected with the liquid inlet end of the ammonia water dosing pump, and the liquid outlet end of the ammonia water dosing pump is connected to the liquid inlet pipeline of the ammonia water neutralizing tank; the magnesium agent feeding device comprises a magnesium agent feeding box and a magnesium agent feeding pump, the liquid outlet end of the magnesium agent feeding box is connected with the liquid inlet end of the magnesium agent feeding pump, and the liquid outlet end of the magnesium agent feeding pump is connected to the liquid inlet pipeline of the ammonia water neutralizing box.

The tubular microfiltration membrane system comprises a tubular membrane water feeding pump, a tubular membrane circulating pump, a tubular membrane device, a tubular membrane water production tank, a neutralization water pump, a titanium hydroxide feed liquid tank, a tubular membrane cleaning device and an automatic control device; the liquid inlet end of the tubular membrane water feeding pump is connected with a titanium hydroxide suspension overflow port of the phosphorus and silicon removing tank through a pipeline, the liquid outlet end of the tubular membrane water feeding pump is connected with the liquid inlet end of the tubular membrane circulating pump, the liquid outlet end of the tubular membrane circulating pump is connected with the liquid inlet of the tubular membrane device, the concentrated liquid outlet of the tubular membrane device is connected to a titanium hydroxide material liquid tank through a pipeline, a material liquid control valve is arranged on the pipeline between the concentrated liquid outlet of the tubular membrane device and the titanium hydroxide material liquid tank, and the pipeline between the material liquid control valve and the concentrated liquid outlet of the tubular membrane device is communicated with the pipeline between the tubular membrane water feeding pump and the tubular membrane circulating pump through a branch pipeline; a product water outlet of the tubular membrane device is connected to a liquid inlet end of the tubular membrane water production tank through a product water outlet pipeline, a product water control valve is arranged on the product water outlet pipeline, a liquid outlet end of the tubular membrane water production tank is connected to a liquid inlet end of a neutralization water pump, and a liquid outlet end of the neutralization water pump is connected with a neutralization device; and the automatic control device is electrically connected with the tubular membrane water feeding pump, the tubular membrane circulating pump, the neutralizing water pump and the water pump in the tubular membrane cleaning device to control the work of each water pump.

Further, the titanium liquid multi-effect evaporation and concentration system comprises a primary preheating device, a secondary preheating device, a primary evaporation device, a secondary evaporation device, a titanium hydroxide discharge pump, a raw steam condensate pump, a secondary steam condensate pump and a non-condensable gas vacuum pump; the one-level preheating device comprises a one-level preheater, the second-level preheating device comprises a second-level preheater, and the one-effect evaporation device comprises: an effect separator, an effect heater, an effect circulating pump, give birth to steam condensate water pitcher, two effect evaporation plant include: the system comprises a two-effect separator, a two-effect heater, a two-effect circulating pump, a secondary steam condensate water tank and a secondary steam condenser; the feed inlet of the primary preheater is connected with a feed inlet pipeline of a titanium hydroxide material, the discharge outlet of the primary preheater is connected with the feed inlet of the secondary preheater, and the discharge outlet of the secondary preheater is connected to a front pipeline of the two-effect circulating pump through a pipeline; the two ends of a front pipeline of the two-effect circulating pump are respectively connected with an inlet of the two-effect circulating pump and a discharge hole of the two-effect separator, an outlet of the two-effect circulating pump is respectively connected with a feed inlet of the two-effect heater and a front pipeline of the one-effect circulating pump through branch pipelines, and the discharge hole of the two-effect heater is connected to a feed inlet of the two-effect separator through a pipeline; the two ends of a front pipeline of the first-effect circulating pump are respectively connected with an inlet of the first-effect circulating pump and a discharge hole of the first-effect separator, an outlet of the first-effect circulating pump is connected to a feed port of the first-effect heater through a pipeline, and a discharge hole of the first-effect heater is connected to a feed port of the first-effect separator through a pipeline; the discharge port of the first-effect separator is connected to a titanium hydroxide discharge pump through a pipeline; a steam inlet of a shell pass of the primary heater is connected with a raw steam inlet pipeline, a condensate outlet of the shell pass of the primary heater is connected to a condensate inlet of a raw steam condensate water tank through a pipeline, a condensate outlet of the raw steam condensate water tank is connected with an inlet of a raw steam condensate water pump through a pipeline, and an outlet of the raw steam condensate water pump is connected to a secondary preheater through a pipeline; a secondary steam outlet at the top of the primary effect separator is connected to a steam inlet of a shell pass of the secondary effect heater through a pipeline, and a condensate outlet of the shell pass of the secondary effect heater is connected to a secondary steam condensate water tank through a pipeline; a steam outlet at the top of the secondary steam condenser is connected to a gas inlet of a shell pass of the secondary steam condenser through a pipeline, a non-condensable gas outlet of the shell pass of the primary heater and a non-condensable gas outlet of the shell pass of the secondary heater are both connected to a gas inlet of the shell pass of the secondary steam condenser through pipelines, a condensate outlet of the shell pass of the secondary steam condenser is connected to a secondary steam condensate water tank through a pipeline, a condensate outlet of the secondary steam condensate water tank is connected to an inlet of a secondary steam condensate water pump through a pipeline, and an outlet of the secondary steam condensate water pump is connected to a primary preheater through a pipeline; and a non-condensable gas outlet of the secondary steam condensate water tank is connected to a non-condensable gas vacuum pump through a pipeline.

Further, the hydrochloric acid neutralization system comprises a neutralization device, an acid adjusting box, a hydrochloric acid storage tank and a hydrochloric acid dosing pump, wherein the neutralization device is provided with a liquid inlet pipeline and a liquid outlet pipeline; the liquid outlet pipeline of the neutralization device is connected with a PH detection device.

Further, the ammonium chloride electrodialysis membrane concentration system comprises an electrodialysis circulating device, a concentrated water output device and a fresh water reverse osmosis membrane desalination device; the electrodialysis circulating device comprises an electrodialysis desalting solution tank, an electrodialysis desalting circulating pump, an electrodialyzer, an electrodialysis concentrated solution circulating pump and an electrodialysis concentrated solution tank; the liquid outlet of the acid adjusting box is connected to the liquid inlet of the electrodialysis desalination liquid box, one liquid outlet of the electrodialysis desalination liquid box is connected to the liquid inlet of the electrodialysis desalination circulating pump, the liquid outlet of the electrodialysis desalination circulating pump is connected to the fresh water side liquid inlet end of the electrodialyzer through a pipeline, and the fresh water side liquid outlet end of the electrodialyzer is connected to the electrodialysis desalination liquid box through a pipeline; one liquid outlet of the electrodialysis concentrated solution tank is connected to the liquid inlet end of an electrodialysis concentrated solution circulating pump, the liquid outlet end of the electrodialysis concentrated solution circulating pump is connected to the concentrated water side liquid inlet end of the electrodialyzer through a pipeline, and the liquid outlet end of the concentrated water side of the electrodialyzer is connected to the liquid inlet of the electrodialysis concentrated solution tank through a pipeline; the other liquid outlet of the electrodialysis concentrated solution box is connected with a concentrated water output device, and the concentrated water output device is connected with an evaporative crystallization system; the upper part of the electrodialysis desalination liquid tank is provided with an overflow port, and the overflow port is connected to a fresh water reverse osmosis membrane desalination device through a pipeline; the concentrated water end of the fresh water reverse osmosis membrane desalination device is connected back to a tubular membrane water production tank of a tubular ultrafiltration membrane concentration system through a pipeline or directly connected back to an electrodialysis desalination tank; the fresh water end of the fresh water reverse osmosis membrane desalination device is connected with a discharge pipeline and is connected to the normal temperature and normal pressure hydrolysis system.

The utility model has the advantages and beneficial effects that: use the utility model discloses equipment can follow olefin polymerization industry waste acid sludge and retrieve titanium in a large number and obtain resourceful byproduct ammonium chloride, and the technology operation requires that low, the rate of recovery is high, the accessory substance of production is few, friendly to the environment, has wide industrial application prospect.

Drawings

The present invention will be further explained with reference to the drawings and examples.

FIG. 1 is a schematic view of the overall structure of the present invention;

FIG. 2 is a schematic view of a normal temperature and pressure hydrolysis apparatus for acid sludge waste in an embodiment of the present invention;

FIG. 3 is a schematic view of an apparatus for removing phosphorus and silicon by catalytic oxidation with ozone and adding magnesium and ammonia water according to an embodiment of the present invention;

FIG. 4 is a schematic view of a tubular microfiltration membrane titanium liquid concentration device according to an embodiment of the present invention;

FIG. 5 is a schematic view of the structure of an ozone reaction tower in the example;

FIG. 6 is a schematic diagram of the multi-effect evaporation and concentration system of the present embodiment;

FIG. 7 is a schematic structural diagram of a hydrochloric acid neutralization system and an electrodialysis membrane concentration system in an embodiment of the present invention;

fig. 8 is a schematic structural diagram of an evaporative crystallization system in an embodiment of the present invention.

Reference numerals: 1-1, a first-stage hydrolysis tank; 1-2, a first-stage hydrolysis circulating pump; 1-3, a first-stage hydrolysis output pump; 1-4. a water inlet valve of a first-stage hydrolysis tank; 1-5, an inlet circulating valve of the first-stage hydrolysis tank; 1-6, outlet discharge valve of first-stage hydrolysis pump; 2-1, a secondary hydrolysis tank; 2-2, a second-stage hydrolysis circulating pump; 2-3, a secondary hydrolysis output pump; 2-4, a water inlet valve of the secondary hydrolysis tank; 2-5, circulating valve at inlet of secondary hydrolysis tank; 2-6, secondary hydrolysis pump outlet discharge valve; 3-1, a sludge box; 3-2, a sludge feeding pump; 3-3, circulating valve of sludge pump outlet; 3-4, a sludge discharge valve; 4-1, plate and frame filter press; 4-2, a filtrate water tank; 4-3, a filtrate water pump; 5. a hydrolysis supernatant collecting device; 5-1, an output pump; 5-2, discharging the hydrolysis supernatant; 6. a clear water inlet pipe; 7. a waste acid sludge feeding device; 8-1, an ozone reaction tower; 8-2. an ozone generator; 8-3, ozone destructor; 8-4, oxidizing the water producing tank; 8-5, a separator; 8-6, ventilating pipeline; 8-7. micron bubble aeration head; 8-8, feeding hydrolysis supernatant; 8-9, water outlet after reaction; 9-1. a filter; 9-2. a water pump of the filter; 10-1, an ammonia water neutralizing tank; 10-2, a phosphorus and silicon removing box; 10-3, neutralizing the dredge pump; 10-4, an ammonia water storage tank; 10-5, ammonia water dosing pump; 10-6. a cosmetic agent feeding box; 10-7, a magnesium agent dosing pump; 10-8, titanium hydroxide suspension; 11-1. a tubular membrane feed pump; 11-2. a tubular membrane circulating pump; 11-3. a tubular membrane device; 11-4. a tubular membrane water production tank; 11-5, a neutralization water pump; 11-6, a titanium hydroxide feed liquid box; 11-7, a tubular membrane backwashing pump; 11-8, a tubular membrane cleaning water tank; 11-9. a tubular membrane cleaning pump; 11-10, a feed liquid control valve; 11-11. tubular membrane water production control valve; 11-12. a feeding pump of the titanium hydroxide crystallizer; 11-13. membrane produced water discharged from the tubular membrane; 11-14, concentrating the titanium hydroxide concentrated solution by a tubular membrane; a1. waste acid sludge inlet of the first-level hydrolysis tank; a2. a liquid inlet of the first-stage hydrolysis tank; a3. a waste acid sludge and circulating water outlet of the primary hydrolysis tank; a4. a supernatant outlet of the first-stage hydrolysis tank; a5. a circulating water inlet of the first-stage hydrolysis tank; b1. a waste acid residue inlet of the secondary hydrolysis tank; b2. a liquid inlet of the first-stage hydrolysis tank; b3. a waste acid sludge and circulating water outlet of the primary hydrolysis tank; b4. a supernatant outlet of the first-stage hydrolysis tank; b5. a circulating water inlet of the first-stage hydrolysis tank; c1. a material circulation inlet of the sludge tank; 12. a primary preheater; 13. a secondary preheater; 14-1. a single effect separator; 14-2. a single effect heater; 14-3, a one-effect circulating pump; 14-4. raw steam condensate water tank; 14-5, a front pipeline of the single-effect circulating pump; 15-1, a two-effect separator; 15-2. a double-effect heater; 15-3, a two-effect circulating pump; 15-4. a secondary steam condensation water tank; 15-5, a front pipeline of a two-effect cycle; 15-6, a secondary steam condenser; 16. a titanium hydroxide discharge pump; 17. a raw steam condensate pump; 18. a secondary steam condensate pump; 19. a noncondensable gas vacuum pump; 20. a titanium hydroxide material liquid inlet pipeline (the material is titanium hydroxide concentrated solution 11-14 after being concentrated by a tubular membrane); 21. raw steam enters the pipeline; 22. the drained condensed water; 23. the evaporated titanium hydroxide concentrated solution; 24. the discharged non-condensable gas; 25-1. a neutralization device; 25-2, an acid adjusting box; 25-3; a hydrochloric acid storage tank; 25-4, a hydrochloric acid dosing pump; 25-5, evaporating condensed water; 25-6. membrane produced water (membrane produced water 11-13 from the discharge of the tubular membrane); 26-1, an electrodialysis desalination liquid tank; 26-2, an electrodialysis desalination circulating pump; 26-3. electrodialyser; 26-4, an electrodialysis concentrated solution circulating pump; 26-5, an electrodialysis concentrated solution tank; 27-1. a thick water tank; 27-2, an ammonium chloride gas-liquid separation feeding pump; 27-3, ammonium chloride concentrated solution; 28-1. collecting box for electroosmosis water production; 28-2, a reverse osmosis feed pump; 28-3, a reverse osmosis safety filter; 28-4 reverse osmosis high pressure pump; 28-5, a reverse osmosis membrane device; 28-6, a reverse osmosis membrane water production tank; 28-7, a reverse osmosis membrane produced water output pump; 28-8, a reverse osmosis membrane cleaning box; 28-9 reverse osmosis membrane cleaning pump; 28-10, cleaning the cartridge filter by the anti-seepage membrane; 28-11 flushing water pump; 28-12. self-water; 28-13, reverse osmosis to obtain concentrated water; 29-1. an electro-osmotic electrode liquid tank; 29-2. an electro-osmotic electrode liquid pump; 30-1. a first preheater; 30-2. a second preheater; 30-3, a pipeline in front of the forced circulation pump; 30-4. forced circulation pump 30-5. forced circulation heater; d1. an inlet of the forced circulation heater tube pass; d2. an outlet of the forced circulation heater tube pass; d3. an inlet of a shell side of the forced circulation heater; d4. an outlet of the shell side of the forced circulation heater; d5. a non-condensable gas outlet of the forced circulation heater; 31-1, a gas-liquid separator; 31-2. a vapor compressor; 31-3, a compressor water spraying tank; 31-4, a spray water pump; 31-5, discharging ammonium chloride; 32-1. a condensate tank; 32-2. a condensate liquid output pump; 32-3, a vacuum pump; 33-A, 33-B and 33-C, cooling and crystallizing tanks; 34-1, a centrifuge; 34-2, a mother liquor tank; 34-3, a mother liquor pump; 34-4, a mother liquor reflux preheater; 35. ammonium chloride concentrate; 36. crystallizing ammonium chloride.

Detailed Description

The first embodiment is as follows:

as shown in figure 1, the equipment for recovering titanium from waste acid sludge in olefin polymerization industry and simultaneously extracting ammonium chloride comprises a normal-temperature normal-pressure hydrolysis system, an ozone catalytic oxidation system, an intermediate filtration system, an ammonia water neutralization, dephosphorization, desilication and magnesium addition system, a tubular microfiltration membrane system, a multi-effect evaporation concentration system, a hydrochloric acid neutralization system, an electrodialysis membrane concentration system and an evaporation crystallization system; the normal temperature and normal pressure hydrolysis system comprises a primary hydrolysis system and a secondary hydrolysis system; the liquid outlet end of the hydrolysate of the normal-temperature normal-pressure hydrolysis system is connected to the liquid inlet end of the ozone catalytic oxidation system through a water pump and a hydrolysis supernatant liquid output pipeline; the liquid outlet end of the ozone catalytic oxidation system is connected to the liquid inlet end of the intermediate filtering system through a pipeline; the liquid outlet end of the intermediate filtering system is connected to the liquid inlet end of the ammonia water neutralization and magnesium addition phosphorus and silicon removal system through a pipeline; the liquid outlet end of the ammonia water neutralization and magnesium addition dephosphorization and desilication system is connected to the titanium hydroxide liquid inlet end of the tubular microfiltration membrane system through a pipeline; the titanium hydroxide liquid outlet end of the tubular microfiltration membrane system is connected to a material liquid inlet of the multi-effect evaporation concentration system through a pipeline; the membrane produced water outlet end of the tubular microfiltration membrane system is connected to the liquid inlet end of the hydrochloric acid neutralization system through a pipeline, and the evaporation condensate outlet of the multi-effect evaporation concentration system is connected to the liquid inlet end of the hydrochloric acid neutralization system through a pipeline; the liquid outlet end of the hydrochloric acid neutralization system is connected with the liquid inlet end of the electrodialysis membrane concentration system through a pipeline; the concentrated solution outlet end of the electrodialysis membrane concentration system is connected with the evaporative crystallization system through a pipeline.

Example two:

the embodiment is a specific optimized scheme based on the first embodiment.

As shown in fig. 2, the normal temperature and pressure hydrolysis system comprises a primary hydrolysis system, a secondary hydrolysis system, a waste acid sludge collection system, a filter pressing system, a hydrolysis supernatant collection device 5, a clear water inlet pipe 6 and a waste acid sludge feeding device 7; the primary hydrolysis system comprises: a primary hydrolysis tank 1-1, a primary hydrolysis circulating pump 1-2 and a primary hydrolysis output pump 1-3; the secondary hydrolysis system comprises: a secondary hydrolysis tank 2-1, a secondary hydrolysis circulating pump 2-2 and a secondary hydrolysis output pump 2-3; the waste acid sludge collecting system comprises: 3-1 of a sludge box and 3-2 of a sludge feed pump; the primary hydrolysis tank 1-1 and the secondary hydrolysis tank 2-1 are respectively provided with a waste acid residue inlet, a waste acid residue and circulating water outlet, a liquid inlet, a supernatant outlet and a circulating water inlet;

a waste acid sludge inlet a1 (the inlet is arranged on one side above the primary hydrolysis tank) of the primary hydrolysis tank 1-1 is connected with the waste acid sludge feeding device 7 (the device can be a feeding pipe and also can be other automatic or manual feeding devices); a liquid inlet a2 of the first-stage hydrolysis tank 1-1 (the liquid inlet is arranged at the other side above the first-stage hydrolysis tank) is connected to the clean water inlet pipe 6 through a branch pipeline, and a first-stage hydrolysis tank water inlet valve 1-4 is arranged on the branch pipeline; the waste acid sludge and circulating water outlet a3 of the first-stage hydrolysis tank 1-1 (the outlet is arranged below the first-stage hydrolysis tank) is connected to the water inlet end of the first-stage hydrolysis circulating pump 1-2 through a pipeline, the water outlet end pipeline of the first-stage hydrolysis circulating pump 1-2 is divided into two branch pipelines (which can be connected by a tee joint) which are respectively connected to the circulating water inlet a5 of the first-stage hydrolysis tank 1-1 (arranged on the upper part of the side wall of the first-stage hydrolysis tank) and the waste acid sludge inlet b1 of the second-stage hydrolysis tank 2-1 (arranged on one side above the second-stage hydrolysis tank), wherein a branch pipeline connecting the water outlet end of the first-stage hydrolysis circulating pump 1-2 with the circulating water inlet a5 of the first-stage hydrolysis tank 1-1 is provided with a first-stage hydrolysis tank inlet circulating valve 1-5, a branch pipeline connected with the waste acid sludge inlet b1 of the second-stage hydrolysis tank 2-1 is provided with a discharge valve 1-6 of a first-stage hydrolysis pump outlet; a supernatant outlet a4 (arranged at the lower part of the side wall of the primary hydrolysis tank) of the primary hydrolysis tank 1-1 is connected to the water inlet end of the primary hydrolysis outward-conveying pump 1-3, and a water outlet pipeline of the primary hydrolysis outward-conveying pump 1-3 is connected to the hydrolysis supernatant collecting device 5;

a liquid inlet b2 (arranged on the other side above the secondary hydrolysis tank) of the secondary hydrolysis tank 2-1 is connected to the clear water inlet pipe 6 through a branch pipeline, and a water inlet valve 2-4 of the secondary hydrolysis tank is arranged on the branch pipeline; a waste acid sludge and circulating water outlet b3 of the second-stage hydrolysis tank 2-1 (arranged below the second-stage hydrolysis tank) is connected to the water inlet end of the second-stage hydrolysis circulating pump 2-2 through a pipeline, the water outlet end pipeline of the second-stage hydrolysis circulating pump 2-2 is divided into two branch pipelines (which can be connected by a tee joint) and respectively connected to a circulating water inlet b5 of the second-stage hydrolysis tank 2-1 (arranged at the upper part of the side wall of the second-stage hydrolysis tank) and an inlet of a sludge tank 3-1 (arranged at the upper part of the sludge tank), wherein a branch pipeline connecting the water outlet end of the second-stage hydrolysis circulating pump 2-2 with the circulating water inlet b5 of the second-stage hydrolysis tank 2-1 is provided with a second-stage hydrolysis tank inlet circulating valve 2-5, a branch pipeline connected with an inlet of the sludge tank 3-1 is provided with a secondary hydrolysis pump outlet discharge valve 2-6; a supernatant outlet b4 of the secondary hydrolysis tank 2-1 is connected to the water inlet end of the secondary hydrolysis outward delivery pump 2-3, and a water outlet pipeline of the secondary hydrolysis outward delivery pump 2-3 is connected to the hydrolysis supernatant collecting device 5;

the export of sludge box 3-1 (set up in the lower part of sludge box) passes through the feed end of tube coupling mud feed pump 3-2, and the discharge end of mud feed pump 3-2 passes through tube coupling to filter-pressing system, and filtration system includes in this embodiment: a plate-and-frame filter press 4-1 (a filter press feed valve is arranged at a feed end), a filtrate water tank 4-2 and a filtrate water pump 4-3; the discharge end of the sludge feed pump 3-2 is connected to the feed end of the plate-and-frame filter press 4-1 through a pipeline, the liquid outlet end of the plate-and-frame filter press 4-1 is connected to the inlet of the filtrate water tank 4-2 through a pipeline, the outlet of the filtrate water tank 4-2 is connected to the water inlet end of the filtrate water pump 4-3 through a pipeline, and the water outlet end of the filtrate water pump 4-3 is connected to the secondary hydrolysis tank 2-1 through a pipeline (the upper end of the side wall of the secondary hydrolysis tank is provided with an independent filtrate inlet).

In the embodiment, a liquid outlet of the hydrolysis supernatant collecting device 5 is connected to a liquid inlet end of an output pump 5-1, and a liquid outlet end of the output pump 5-1 is connected to an oxidation catalysis impurity removal system.

As shown in fig. 3, the catalytic ozonation system comprises an ozone reaction tower 8-1 (see fig. 5 for a specific structure), an ozone generator 8-2, an ozone destructor 8-3 and an oxidation water production tank 8-4; the top of an ozone reaction tower 8-1 is provided with an ozone destructor 8-3, the inside of the ozone reaction tower 8-1 is provided with an upper layer of clapboard 8-5 with holes and a lower layer of clapboard 8-5 with holes, a catalyst packing layer is arranged between the two layers of clapboards, the bottom of the ozone reaction tower 8-1 is fixed with an air duct 8-6, the air duct 8-6 is provided with a plurality of micron bubble aeration heads 8-7, and an air inlet interface of the air duct 8-6 is connected with an air duct of an ozone generator 8-2; a hydrolysis supernatant inlet 8-8 is arranged on the side wall of the ozone reaction tower 8-1 below the catalyst packing layer, the inlet is connected to the liquid outlet end of the output pump 5-1, a reacted water outlet 8-9 is arranged on the side wall of the ozone reaction tower 8-1 above the catalyst packing layer, and the reacted water outlet 8-9 is connected with a water inlet of the oxidation product water tank 8-4 through a pipeline.

The intermediate filtering system comprises a filter 9-1 and a filter water feeding pump 9-2 connected with the filter 9-1, a water outlet of the oxidation product water tank 8-4 is connected with a water inlet end of the filter water feeding pump 9-2 through a pipeline, a water outlet end of the filter water feeding pump 9-2 is connected with a water inlet end of the filter 9-1, and a water outlet end of the filter 9-1 is connected with an ammonia water neutralization and magnesium addition phosphorus and silicon removal system.

The ammonia water neutralization and magnesium adding phosphorus and silicon removal system comprises an ammonia water neutralization tank 10-1, a phosphorus and silicon removal tank 10-2, a neutralization sludge discharge pump 10-3, an ammonia water feeding device and a magnesium agent feeding device, wherein the phosphorus and silicon removal tank is communicated with the ammonia water neutralization tank, the bottom of the phosphorus and silicon removal tank is conical, a water inlet of the ammonia water neutralization tank 10-1 is connected with a water outlet end of a filter 9-1, the ammonia water neutralization tank 10-1 is connected with the phosphorus and silicon removal tank 10-2 through an overflow port, a precipitation outlet is formed in the bottom of the phosphorus and silicon removal tank 10-2 and is connected to the neutralization sludge discharge pump 10-3 through a pipeline, a titanium hydroxide suspension overflow port is formed in the side wall of the phosphorus and silicon removal tank 10-2, and the titanium hydroxide suspension overflow port is connected to the micro-filtration tubular membrane system. In the embodiment, the ammonia water adding device comprises an ammonia water storage tank 10-4 and an ammonia water dosing pump 10-5, wherein the liquid outlet end of the ammonia water storage tank 10-4 is connected with the liquid inlet end of the ammonia water dosing pump 10-5, and the liquid outlet end of the ammonia water dosing pump 10-5 is connected to the liquid inlet pipeline of the ammonia water neutralizing tank 10-1; the magnesium agent feeding device comprises a magnesium agent feeding box 10-6 and a magnesium agent feeding pump 10-7, wherein the liquid outlet end of the magnesium agent feeding box 10-6 is connected with the liquid inlet end of the magnesium agent feeding pump 10-7, and the liquid outlet end of the magnesium agent feeding pump 10-7 is connected with the liquid inlet pipeline of the ammonia water neutralizing box 10-1.

As shown in fig. 4, the tubular microfiltration membrane system comprises a tubular membrane water feed pump 11-1, a tubular membrane circulating pump 11-2, a tubular membrane device 11-3, a tubular membrane water production tank 11-4, a neutralization water pump 11-5, a titanium hydroxide feed liquid tank 11-6, a tubular membrane cleaning device and an automatic control device; the liquid inlet end of the tubular membrane water feed pump 11-1 is connected with the titanium hydroxide suspension overflow port of the phosphorus and silicon removal tank 10-2 through a pipeline, the liquid outlet end of the tubular membrane water feed pump 11-1 is connected with the liquid inlet end of the tubular membrane circulating pump 11-2, the liquid outlet end of the tubular membrane circulating pump 11-2 is connected with the liquid inlet of the tubular membrane device 11-3, the concentrated solution outlet of the tubular membrane device 11-3 is connected to a titanium hydroxide feed solution tank 11-6 through a pipeline, a feed liquid control valve 11-10 is arranged on a pipeline between the concentrated liquid outlet of the tubular membrane device 11-3 and the titanium hydroxide feed liquid tank 11-6, and a pipeline between the feed liquid control valve 11-10 and the concentrated liquid outlet of the tubular membrane device 11-3 is communicated with a pipeline between the tubular membrane water feed pump 11-1 and the tubular membrane circulating pump 11-2 through a branch pipeline; a product water outlet of the tubular membrane device 11-3 is connected to a liquid inlet end of a tubular membrane water production tank 11-4 through a product water outlet pipeline, a tubular membrane water production water control valve 11-11 is arranged on the product water outlet pipeline, a liquid outlet end of the tubular membrane water production tank 11-4 is connected to a liquid inlet end of a neutralization water pump 11-5, and a liquid outlet end of the neutralization water pump 11-5 is connected with a neutralization device; the automatic control device is electrically connected with the tubular membrane water feeding pump 11-1, the tubular membrane circulating pump 11-2, the neutralization water pump 11-5 and the water pump in the tubular membrane cleaning device to control the work of each water pump.

The tubular membrane cleaning device comprises a tubular membrane backwashing pump 11-7 and a chemical cleaning device, wherein the chemical cleaning device comprises a tubular membrane cleaning water tank 11-8 and a tubular membrane cleaning pump 11-9; the liquid outlet end of the tubular membrane water production tank 11-4 is provided with a branch pipeline connected with the liquid inlet end of the tubular membrane backwashing pump 11-7, the liquid outlet end of the tubular membrane backwashing pump 11-7 is connected with the product water outlet pipeline of the tubular membrane device 11-3, and the connection point is positioned between the product water outlet of the tubular membrane device 11-3 and the product water control valve 11-11; the liquid outlet of the tubular membrane cleaning water tank 11-8 is connected with the liquid inlet end of the tubular membrane cleaning pump 11-9, the liquid outlet end of the tubular membrane cleaning pump 11-9 is connected with a liquid inlet pipeline between the tubular membrane circulating pump 11-2 and the liquid inlet of the tubular membrane device 11-3 through a pipeline, and a branch pipeline is respectively divided from the concentrated solution outlet and the product water outlet of the tubular membrane device 11-3 and is connected with the liquid inlet of the tubular membrane cleaning water tank 11-8.

The operation flow of the device in fig. 3 is: the hydrolysis supernatant is introduced into the bottom of an ozone reaction tower 8-1, ozone generated by an ozone generator 8-2 is sent to the bottom of the ozone reaction tower through an aeration device to react with the hydrolysis supernatant, the reacted materials flow through a catalyst in the tower and overflow to an oxidation water production tank 8-4, the liquid level of the oxidation water production tank 8-4 rises to a set liquid level value, and a filter water feeding pump 9-2 is started to convey the reacted materials to a filter 9-1; adding ammonia water into the filtrate filtered by the filter 9-1, and feeding the filtrate into an ammonia water neutralizing tank 10-1 for neutralization; adding a magnesium agent (magnesium chloride) before the filtrate filtered by the filter enters an ammonia water neutralization tank 10-1; the materials neutralized by the ammonia water neutralization tank 10-1 overflow to the phosphorus and silicon removal tank 10-2, the generated calcium phosphate, calcium silicate, magnesium silicate and the like are precipitated to the bottom of the phosphorus and silicon removal tank 10-2 and are conveyed to a sludge tank through a neutralization sludge discharge pump 10-3, and the overflowed titanium hydroxide suspension enters a tubular membrane microfiltration system.

The operation flow of the device in fig. 4 is: titanium hydroxide suspension flowing out of the phosphorus and silicon removal tank is lifted by a tubular membrane water feed pump 11-1 and then enters a tubular membrane device 11-3 for concentration, water coming from the tubular membrane water feed pump 11-1 is mixed with circulating concentrated solution and then is lifted by a tubular membrane circulating pump 11-2 to the tubular membrane device 11-3, and the concentrate of the tubular membrane device is discharged to a titanium hydroxide feed solution tank 11-6; and the product water of the tubular membrane device enters a tubular membrane water production tank 11-4 and is discharged through a neutralization water pump 11-5. The pore size of the tubular membrane filter in the tubular membrane device is 0.05 micron. The tubular membrane device 11-3 performs backwashing once by adopting a tubular membrane backwashing pump 11-7 every filtering period of time so as to recover membrane flux. Membrane systems require periodic chemical cleaning after a period of operation to restore the membrane elements to performance. After cleaning agents such as acid, alkali and the like are prepared in the tubular membrane cleaning water tank 11-8 according to a certain concentration, the cleaning agents are lifted by the tubular membrane cleaning pump 11-9 and then enter the membrane system to clean the membrane surface, and the cleaned water flows back to the tubular membrane cleaning water tank 11-8 through a pipeline for recycling.

As shown in fig. 6, in the titanium liquid multi-effect evaporation concentration system: one-level preheating device includes one-level preheater 12, second grade preheating device includes second grade preheater 13, an effect evaporation plant includes: the device comprises a primary-effect separator 14-1, a primary-effect heater 14-2, a primary-effect circulating pump 14-3 and a raw steam condensate water tank 14-4, wherein the secondary-effect evaporation device comprises: a double-effect separator 15-1, a double-effect heater 15-2, a double-effect circulating pump 15-3, a secondary steam condensate water tank 15-4 and a secondary steam condenser 15-6;

a feed inlet of the primary preheater 12 is connected with a titanium hydroxide material feed inlet pipeline 20 (the titanium hydroxide material feed inlet pipeline 20 is connected with a liquid outlet end of the tubular membrane microfiltration system, namely is connected with a titanium hydroxide crystallizer feed pump 11-12, and the titanium hydroxide crystallizer feed pump is connected with an outlet of a titanium hydroxide material liquid tank 16), a discharge outlet of the primary preheater 12 is connected with a feed inlet of the secondary preheater 13, and a discharge outlet of the secondary preheater 13 is connected to a front pipeline 15-5 of the secondary circulation pump through a pipeline; the two ends of a front pipeline 15-5 of the two-effect circulating pump are respectively connected with an inlet of the two-effect circulating pump 15-3 and a discharge hole of the two-effect separator 15-1, an outlet of the two-effect circulating pump 15-3 is respectively connected with a feed inlet of the two-effect heater 15-2 and a front pipeline 14-5 of the one-effect circulating pump through branch pipelines (a valve is arranged on a pipeline between the outlet of the two-effect circulating pump 15-3 and the front pipeline 14-5 of the one-effect circulating pump), and the discharge hole of the two-effect heater 15-2 is connected to the feed inlet of the two-effect separator 15-1 through a pipeline; two ends of a front pipeline 14-5 of the first-effect circulating pump are respectively connected with an inlet of the first-effect circulating pump 14-3 and a discharge hole of the first-effect separator 14-1, an outlet of the first-effect circulating pump 14-3 is connected to a feed hole of the first-effect heater 14-2 through a pipeline, and a discharge hole of the first-effect heater 14-2 is connected to a feed hole of the first-effect separator 14-1 through a pipeline; the discharge port of the first-effect separator 14-1 is connected to a titanium hydroxide discharge pump 16 through a pipeline;

a steam inlet of a shell pass of the primary heater 14-2 is connected with a raw steam inlet pipeline 21, a condensate outlet of the shell pass of the primary heater is connected to a condensate inlet of a raw steam condensate water tank 14-4 through a pipeline, a condensate outlet of the raw steam condensate water tank 14-4 is connected with an inlet of a raw steam condensate water pump 17 through a pipeline, an outlet of the raw steam condensate water pump 17 is connected to a water inlet of a shell pass of the secondary preheater 13 through a pipeline, and a water outlet of the shell pass of the secondary preheater 13 is connected to a tubular membrane water production tank through a pipeline;

a secondary steam outlet at the top of the primary separator 14-1 is connected to a steam inlet of a secondary heater 15-2 shell pass through a pipeline, and a condensate outlet of the secondary heater 15-2 shell pass is connected to a secondary steam condensate water tank 15-4 through a pipeline; a steam outlet at the top of the secondary separator 15-1 is connected to a gas inlet of a secondary steam condenser 15-6 shell pass through a pipeline, a non-condensable gas outlet of a primary heater 14-2 shell pass and a non-condensable gas outlet of a secondary heater 15-2 shell pass are connected to a gas inlet of a secondary steam condenser 15-6 shell pass through pipelines, a condensate outlet of the shell pass of the secondary steam condenser 15-6 is connected to a secondary steam condensate water tank 15-4 through a pipeline, a condensate water outlet of the secondary steam condensate water tank 15-4 is connected to an inlet of a secondary steam condensate water pump 18 through a pipeline, an outlet of the secondary steam condensate water pump 18 is connected to a water inlet of a primary preheater 12 shell pass through a pipeline, and a water outlet of the primary preheater 12 shell pass is connected to a tubular membrane water production tank through a pipeline; the non-condensable gas outlet of the secondary steam condensate water tank 15-4 is connected to a non-condensable gas vacuum pump 19 through a pipeline. The outlet of the titanium hydroxide discharge pump 16 is provided with a branch pipeline which is connected to the primary separator 14-1.

As shown in fig. 7, the hydrochloric acid neutralization system comprises a neutralization device 25-1, an acid adjustment tank 25-2, a hydrochloric acid storage tank 25-3 and a hydrochloric acid dosing pump 25-4, wherein the neutralization device is provided with a liquid inlet pipeline and a liquid outlet pipeline, a liquid outlet of the hydrochloric acid storage tank 25-3 is connected with a liquid inlet of the hydrochloric acid dosing pump 25-4, a liquid outlet of the hydrochloric acid dosing pump 25-4 is connected with the liquid inlet pipeline of the hydrochloric acid neutralization device 25-1 through a pipeline, and a liquid outlet pipeline of the neutralization device 25-1 is connected with the acid adjustment tank 25-2; the liquid outlet pipeline of the neutralization device is connected with a PH detection device.

The ammonium chloride electrodialysis membrane concentration system comprises an electrodialysis circulating device, a concentrated water output device and a fresh water reverse osmosis membrane desalination device.

The electrodialysis circulating device comprises an electrodialysis desalting solution tank 26-1, an electrodialysis desalting circulating pump 26-2, an electrodialyzer 26-3, an electrodialysis concentrated solution circulating pump 26-4 and an electrodialysis concentrated solution tank 26-5; a liquid outlet of the acid adjusting tank 26-2 is connected to a liquid inlet of the electrodialysis desalination liquid tank 26-1, a liquid outlet of the electrodialysis desalination liquid tank 26-1 is connected to a liquid inlet of the electrodialysis desalination circulating pump 26-2, a liquid outlet of the electrodialysis desalination circulating pump 26-2 is connected to a fresh water side liquid inlet end of the electrodialyzer 26-3 through a pipeline, and a fresh water side liquid outlet end of the electrodialyzer 26-3 is connected to the electrodialysis desalination liquid tank 26-1 through a pipeline; one liquid outlet of the electrodialysis concentrated solution tank 26-5 is connected to the liquid inlet end of an electrodialysis concentrated solution circulating pump 26-4, the liquid outlet end of the electrodialysis concentrated solution circulating pump 26-4 is connected to the concentrated water side liquid inlet end of the electrodialyzer 26-3 through a pipeline, and the liquid outlet end of the concentrated water side of the electrodialyzer 26-3 is connected back to the liquid inlet of the electrodialysis concentrated solution tank 26-5 through a pipeline; the other liquid outlet of the electrodialysis concentrated solution tank 26-5 is connected with a concentrated water output device, and the concentrated water output device is connected with an evaporative crystallization system; the upper part of the electrodialysis desalination liquid tank 26-1 is provided with an overflow port, and the overflow port is connected to a fresh water reverse osmosis membrane desalination device through a pipeline; the concentrated water end of the fresh water reverse osmosis membrane desalination device is connected back to a tubular membrane water generating tank 11-4 of a tubular ultrafiltration membrane concentration system through a pipeline or directly connected back to an electrodialysis desalination liquid tank 26-1; the fresh water end of the fresh water reverse osmosis membrane desalination device is connected with a discharge pipeline and is connected to the normal temperature and normal pressure hydrolysis system.

The concentrated water output device comprises a concentrated water tank 27-1 and an ammonium chloride gas-liquid separation feed pump 27-2, the other liquid outlet of the electrodialysis concentrated solution tank 26-5 is connected with the liquid inlet of the concentrated water tank 27-1, and the liquid outlet of the concentrated water tank 27-1 is connected with the ammonium chloride gas-liquid separation feed pump 27-2.

The fresh water reverse osmosis membrane desalination device comprises an electroosmosis water production collection box 28-1, a reverse osmosis water feed pump 28-2, a reverse osmosis security filter 28-3, a reverse osmosis high-pressure pump 28-4, a reverse osmosis membrane (RO) device 28-5, a reverse osmosis membrane water production box 28-6, a reverse osmosis membrane water production output pump 28-7 and a reverse osmosis membrane cleaning device; the upper part of the electrodialysis desalination liquid tank 26-1 is provided with an overflow port which is connected with an electroosmosis water production collecting tank 28-1 through a pipeline, the water outlet of the electroosmosis water production collecting tank 28-1 is connected with the water inlet of a reverse osmosis water feed pump 28-2, the water outlet of the reverse osmosis water feed pump 28-2 is connected with the water inlet of a reverse osmosis safety filter 28-3, the water outlet of the reverse osmosis safety filter 28-3 is connected with the water inlet of a reverse osmosis high-pressure pump 28-4, the water outlet of the reverse osmosis high-pressure pump 28-4 is connected with the liquid inlet end of a reverse osmosis membrane device 28-5, the membrane water production outlet of the reverse osmosis membrane device 28-5 is connected with the water inlet of a reverse osmosis membrane water production tank 28-6, and the water outlet of the reverse osmosis membrane water production tank 28-6 is connected with a reverse osmosis membrane water production outward delivery pump 28-7; and a concentrated water outlet of the reverse osmosis membrane device 28-5 is connected to a tubular membrane water production tank of the tubular ultrafiltration membrane concentration system and is directly connected to an electrodialysis desalination liquid tank. The reverse osmosis membrane cleaning device comprises a reverse osmosis membrane cleaning box 28-8, a reverse osmosis membrane cleaning pump 28-9, an anti-seepage membrane cleaning cartridge filter 28-10 and a flushing water pump 28-11.

And an electrode liquid adding device is connected with the electrodialyzer through a pipeline to add the electrode liquid. The electrode liquid adding device comprises an electro-osmotic electrode liquid tank 29-1 and an electro-osmotic electrode liquid pump 29-2.

As shown in fig. 8, the ammonium chloride evaporative crystallization system includes: feeding preheating device, evaporation plant, crystallization device, discharging device and condensing equipment:

the feed preheating device comprises a feed pump, a first preheater 30-1, a second preheater 30-2, a forced circulation pump 30-4 and a forced circulation heater 30-5, a discharge port of the feed pump is connected with a liquid inlet of a first preheater 30-1 through a pipeline, a liquid outlet of the first preheater 30-1 is connected with a liquid inlet of a second preheater 30-2 through a pipeline, a liquid outlet of the second preheater 30-2 is connected with a front pipeline 30-3 of a forced circulation pump, the tail end of the front pipeline 30-3 of the forced circulation pump is connected with a liquid inlet of a forced circulation pump 30-4, a liquid outlet of the forced circulation pump 30-4 is connected with an inlet d1 of a tube pass of the forced circulation heater 30-5, and an outlet d2 of the tube pass of the forced circulation heater 30-5 is connected with a liquid inlet of a gas-liquid separator 31-1 through a pipeline; a pipeline between the forced circulation pump 30-4 and the forced circulation heater 30-5 is provided with a density sensor for measuring the density of the ammonium chloride solution;

the evaporation device comprises a gas-liquid separator 31-1, a vapor compressor 31-2, a compressor water spraying tank 31-3 and a spray water pump 31-4; the top of the gas-liquid separator 31-1 is connected with a steam-liquid compressor 31-2, the liquid outlet of the compressor water spraying tank 31-3 is connected with a spray water pump 31-4, and the liquid outlet of the spray water pump 31-4 is connected to a constant-flow water supply pipeline of the steam compressor 31-2 through a pipeline; the steam outlet of the steam compressor 31-2 is connected with the inlet d3 of the shell pass of the forced circulation heater 30-5 through a pipeline, and the outlet d4 of the shell pass of the forced circulation heater 30-5 is connected with the liquid inlet of the condensate tank 32-1 through a pipeline; a liquid outlet at the bottom of the gas-liquid separator 31-1 is connected with an inlet of an ammonium chloride discharge pump 31-5, and an outlet of the ammonium chloride discharge pump 31-5 is connected to a crystallization device through a pipeline; the non-condensable gas outlet d5 of the forced circulation heater 30-5 is connected to the vacuum pump 32-3 through a pipeline;

the crystallization device comprises a plurality of cooling crystallization tanks 33-A, 33-B and 33-C which are connected through pipelines, the cooling crystallization tanks are provided with circulating cooling water devices, and the pipelines among the cooling crystallization tanks are provided with valves;

the discharging device comprises a centrifuge 34-1, a mother liquor tank 34-2, a mother liquor pump 34-3 and a mother liquor reflux preheater 34-4; the outlet of the cooling crystallization tank is connected with the centrifuge 34-1; a mother liquor outlet of the centrifuge 34-1 is connected to a mother liquor tank 34-2 through a pipeline, an outlet of the mother liquor tank 34-2 is connected to a liquid inlet of a tube pass of a mother liquor reflux preheater 34-4 through a pipeline, a liquid outlet of the tube pass of the mother liquor reflux preheater 34-4 is connected to an inlet of a mother liquor pump 34-3 through a pipeline, and an outlet of the mother liquor pump 34-3 is connected to a front pipeline 30-3 of the forced circulation pump through a pipeline; a liquid inlet of a shell side of the mother liquor reflux preheater 34-4 is connected with an external hot steam pipeline;

the condensing device comprises a condensate tank 32-1 and a condensate outward-conveying pump 32-2; a liquid outlet of a shell pass of the mother liquor reflux preheater 32-4 is connected to a liquid inlet of the condensate tank 32-1 through a pipeline; the liquid outlet of the condensate tank 32-1 is connected with the liquid inlet of the condensate outward-conveying pump 32-2, and the liquid outlet of the condensate outward-conveying pump 32-2 is respectively connected with the compressor water spraying tank 31-3 and the tubular membrane water production tank through pipelines.

Finally, it should be noted that the above only illustrates the technical solution of the present invention and not by limitation, and although the present invention has been described in detail with reference to preferred arrangements, a person skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. The equipment for recovering titanium from the waste acid sludge in the olefin polymerization industry and simultaneously extracting ammonium chloride is characterized in that: the system comprises a normal-temperature normal-pressure hydrolysis system, an ozone catalytic oxidation system, an intermediate filtration system, an ammonia water neutralization dephosphorization desilicification and magnesium addition system, a tubular microfiltration membrane system, a multi-effect evaporation concentration system, a hydrochloric acid neutralization system, an electrodialysis membrane concentration system and an evaporation crystallization system; the normal temperature and normal pressure hydrolysis system comprises a primary hydrolysis system and a secondary hydrolysis system; the liquid outlet end of the hydrolysate of the normal-temperature normal-pressure hydrolysis system is connected to the liquid inlet end of the ozone catalytic oxidation system through a water pump and a hydrolysis supernatant liquid output pipeline; the liquid outlet end of the ozone catalytic oxidation system is connected to the liquid inlet end of the intermediate filtering system through a pipeline; the liquid outlet end of the intermediate filtering system is connected to the liquid inlet end of the ammonia water neutralization and magnesium addition phosphorus and silicon removal system through a pipeline; the liquid outlet end of the ammonia water neutralization and magnesium addition dephosphorization and desilication system is connected to the titanium hydroxide liquid inlet end of the tubular microfiltration membrane system through a pipeline; the titanium hydroxide liquid outlet end of the tubular microfiltration membrane system is connected to a material liquid inlet of the multi-effect evaporation concentration system through a pipeline; the membrane produced water outlet end of the tubular microfiltration membrane system is connected to the liquid inlet end of the hydrochloric acid neutralization system through a pipeline, and the evaporation condensate outlet of the multi-effect evaporation concentration system is connected to the liquid inlet end of the hydrochloric acid neutralization system through a pipeline; the liquid outlet end of the hydrochloric acid neutralization system is connected with the liquid inlet end of the electrodialysis membrane concentration system through a pipeline; the concentrated solution outlet end of the electrodialysis membrane concentration system is connected with the evaporative crystallization system through a pipeline.

2. The apparatus for recovering titanium and simultaneously extracting ammonium chloride from acid sludge in olefin polymerization industry according to claim 1, wherein: the normal temperature and pressure hydrolysis system comprises a primary hydrolysis system, a secondary hydrolysis system, a waste acid residue collecting system, a filter pressing system, a hydrolysis supernatant collecting device (5), a clear water inlet pipe (6) and a waste acid residue feeding device (7);

the primary hydrolysis system comprises: a first-stage hydrolysis tank (1-1), a first-stage hydrolysis circulating pump (1-2) and a first-stage hydrolysis output pump (1-3); the secondary hydrolysis system comprises: a secondary hydrolysis tank (2-1), a secondary hydrolysis circulating pump (2-2) and a secondary hydrolysis output pump (2-3); the waste acid sludge collecting system comprises: a sludge box (3-1) and a sludge feed pump (3-2);

the primary hydrolysis tank (1-1) and the secondary hydrolysis tank (2-1) are respectively provided with a waste acid residue inlet, a waste acid residue and circulating water outlet, a liquid inlet, a hydrolysis supernatant outlet and a circulating water inlet;

a waste acid residue inlet of the primary hydrolysis tank (1-1) is connected with the waste acid residue feeding device (7); a liquid inlet of the first-stage hydrolysis tank (1-1) is connected to the clear water inlet pipe (6) through a branch pipeline, and a first-stage hydrolysis tank water inlet valve (1-4) is arranged on the branch pipeline; the waste acid sludge and circulating water outlet of the first-stage hydrolysis tank (1-1) is connected to the water inlet end of the first-stage hydrolysis circulating pump (1-2) through a pipeline, the water outlet end pipeline of the first-stage hydrolysis circulating pump (1-2) is divided into two branch pipelines which are respectively connected to the circulating water inlet of the first-stage hydrolysis tank (1-1) and the waste acid sludge inlet of the second-stage hydrolysis tank (2-1), wherein the branch pipeline connected with the circulating water inlet of the first-stage hydrolysis tank (1-1) is provided with a first-stage hydrolysis tank inlet circulating valve (1-5), and the branch pipeline connected with the waste acid sludge inlet of the second-stage hydrolysis tank (2-1) is provided with a first-stage hydrolysis pump outlet discharge valve (1-6); a supernatant outlet of the primary hydrolysis tank (1-1) is connected to a water inlet end of the primary hydrolysis output pump (1-3), and a water outlet pipeline of the primary hydrolysis output pump (1-3) is connected to a hydrolysis supernatant collecting device (5);

a liquid inlet of the secondary hydrolysis tank (2-1) is connected to the clear water inlet pipe (6) through a branch pipeline, and a water inlet valve (2-4) of the secondary hydrolysis tank is arranged on the branch pipeline; the waste acid sludge and circulating water outlet of the second-stage hydrolysis tank (2-1) is connected to the water inlet end of the second-stage hydrolysis circulating pump (2-2) through a pipeline, the water outlet end pipeline of the second-stage hydrolysis circulating pump (2-2) is divided into two branch pipelines which are respectively connected to the circulating water inlet of the second-stage hydrolysis tank (2-1) and the inlet of the sludge tank (3-1), wherein the branch pipeline connected with the circulating water inlet of the second-stage hydrolysis tank (2-1) is provided with a second-stage hydrolysis tank inlet circulating valve (2-5), and the branch pipeline connected with the inlet of the sludge tank (3-1) is provided with a second-stage hydrolysis pump outlet discharge valve (2-6); a supernatant outlet of the secondary hydrolysis tank (2-1) is connected to a water inlet end of the secondary hydrolysis outward delivery pump (2-3), and a water outlet pipeline of the secondary hydrolysis outward delivery pump (2-3) is connected to a hydrolysis supernatant collecting device (5);

an outlet of the sludge tank (3-1) is connected with a feed end of a sludge feed pump (3-2), a discharge end of the sludge feed pump (3-2) is connected to a filter pressing system through a pipeline, and a filtrate discharge pipeline of the filter pressing system is connected to the secondary hydrolysis tank (2-1).

3. The apparatus for recovering titanium and simultaneously extracting ammonium chloride from acid sludge in olefin polymerization industry according to claim 1, wherein: the ozone catalytic oxidation system comprises an ozone reaction tower (8-1), an ozone generator (8-2), an ozone destructor (8-3) and an oxidation water production tank (8-4); the top of the ozone reaction tower (8-1) is provided with an ozone destructor (8-3), the inside of the ozone reaction tower (8-1) is provided with an upper layer of clapboard (8-5) with holes and a lower layer of clapboard with holes, a catalyst packing layer is arranged between the two layers of clapboards, the bottom of the ozone reaction tower (8-1) is fixed with an air duct (8-6), the air duct (8-6) is provided with a plurality of micron bubble aeration heads (8-7), and an air inlet interface of the air duct (8-6) is connected with an air duct of the ozone generator (8-2); a hydrolysis supernatant inlet (8-8) is arranged on the side wall of the ozone reaction tower (8-1) below the catalyst packing layer, and the hydrolysis supernatant inlet (8-8) is connected to a hydrolysate liquid outlet end of the normal-temperature normal-pressure hydrolysis system through a pipeline; a water outlet (8-9) after reaction is arranged on the side wall of the ozone reaction tower (8-1) above the catalyst packing layer, and the water outlet (8-9) after reaction is connected with a water inlet of the oxidation product water tank (8-4) through a pipeline;

the middle filtering system comprises a filter (9-1) and a filter water feeding pump (9-2) connected with the filter, a water outlet of the oxidation product water tank (8-4) is connected with a water inlet end of the filter water feeding pump (9-2) through a pipeline, a water outlet end of the filter water feeding pump (9-2) is connected with a water inlet end of the filter (9-1), and a water outlet end of the filter (9-1) is connected with the ammonia water neutralization and magnesium addition phosphorus and silicon removal system;

the ammonia water neutralization and magnesium adding phosphorus and silicon removal system comprises an ammonia water neutralization tank (10-1), a phosphorus and silicon removal tank (10-2) which is communicated with the ammonia water neutralization tank and has a conical bottom, a neutralization sludge discharge pump (10-3), an ammonia water feeding device and a magnesium agent feeding device, wherein a water inlet of the ammonia water neutralization tank (10-1) is connected with a water outlet end of the filter (9-1), the ammonia water neutralization tank (10-1) is connected with the phosphorus and silicon removal tank (10-2) through an overflow port, a precipitation outlet is arranged at the bottom of the phosphorus and silicon removal tank (10-2) and is connected to the neutralization sludge discharge pump (10-3) through a pipeline, a titanium hydroxide suspension overflow port is arranged on the side wall of the phosphorus and silicon removal tank (10-2), and the titanium hydroxide suspension overflow port is connected to the tubular microfiltration membrane system; the ammonia water adding device comprises an ammonia water storage tank (10-4) and an ammonia water dosing pump (10-5), wherein the liquid outlet end of the ammonia water storage tank (10-4) is connected with the liquid inlet end of the ammonia water dosing pump (10-5), and the liquid outlet end of the ammonia water dosing pump (10-5) is connected to the liquid inlet pipeline of the ammonia water neutralizing tank (10-1); the magnesium agent feeding device comprises a magnesium agent feeding box (10-6) and a magnesium agent feeding pump (10-7), wherein the liquid outlet end of the magnesium agent feeding box (10-6) is connected with the liquid inlet end of the magnesium agent feeding pump (10-7), and the liquid outlet end of the magnesium agent feeding pump (10-7) is connected to the liquid inlet pipeline of the ammonia water neutralizing box (10-1).

4. The apparatus for recovering titanium and simultaneously extracting ammonium chloride from acid sludge in olefin polymerization industry according to claim 3, wherein: the tubular microfiltration membrane system comprises a tubular membrane water feeding pump (11-1), a tubular membrane circulating pump (11-2), a tubular membrane device (11-3), a tubular membrane water production tank (11-4), a neutralization water pump (11-5), a titanium hydroxide feed liquid tank (11-6), a tubular membrane cleaning device and an automatic control device; the liquid inlet end of the tubular membrane water feeding pump (11-1) is connected with a titanium hydroxide suspension overflow port of the phosphorus and silicon removing tank (10-2) through a pipeline, the liquid outlet end of the tubular membrane water feeding pump (11-1) is connected with the liquid inlet end of the tubular membrane circulating pump (11-2), the liquid outlet end of the tubular membrane circulating pump (11-2) is connected with the liquid inlet of the tubular membrane device (11-3), the concentrated liquid outlet of the tubular membrane device (11-3) is connected to the titanium hydroxide material liquid tank (11-6) through a pipeline, a material liquid control valve (11-10) is arranged on the pipeline between the concentrated liquid outlet of the tubular membrane device (11-3) and the titanium hydroxide material liquid tank (11-6), and the pipeline between the material liquid control valve (11-10) and the concentrated liquid outlet of the tubular membrane device (11-3) is communicated with the tubular membrane water feeding pump (11-1) and the tubular membrane circulating pump (11-2) through a branch pipeline (11-2) a line between; a product water outlet of the tubular membrane device (11-3) is connected to a liquid inlet end of the tubular membrane water production tank (11-4) through a product water outlet pipeline, a product water control valve (11-11) is arranged on the product water outlet pipeline, a liquid outlet end of the tubular membrane water production tank (11-4) is connected to a liquid inlet end of a neutralization water pump (11-5), and a liquid outlet end of the neutralization water pump (11-5) is connected with a hydrochloric acid neutralization device; the automatic control device is electrically connected with the tubular membrane water feeding pump (11-1), the tubular membrane circulating pump (11-2), the neutralizing water pump (11-5) and the water pump in the tubular membrane cleaning device to control the work of each water pump.

5. The apparatus for recovering titanium and simultaneously extracting ammonium chloride from acid sludge in olefin polymerization industry according to claim 1, wherein: the multi-effect evaporation concentration system comprises a primary preheating device, a secondary preheating device, a primary evaporation device, a secondary evaporation device, a titanium hydroxide discharge pump (16), a raw steam condensate pump (17), a secondary steam condensate pump (18) and a non-condensable gas vacuum pump (19);

the one-level preheating device comprises a one-level preheater (12), the second-level preheating device comprises a second-level preheater (13), and the one-effect evaporation device comprises: the device comprises a single-effect separator (14-1), a single-effect heater (14-2), a single-effect circulating pump (14-3) and a raw steam condensate water tank (14-4), and the double-effect evaporation device comprises: a double-effect separator (15-1), a double-effect heater (15-2), a double-effect circulating pump (15-3), a secondary steam condensate water tank (15-4) and a secondary steam condenser (15-6);

a feed inlet of the primary preheater (12) is connected with a titanium hydroxide material inlet pipeline (20), a discharge outlet of the primary preheater (12) is connected with a feed inlet of the secondary preheater (13), and a discharge outlet of the secondary preheater (13) is connected to a front pipeline (15-5) of the two-effect circulating pump through a pipeline; the two ends of a front pipeline (15-5) of the double-effect circulating pump are respectively connected with an inlet of the double-effect circulating pump (15-3) and a discharge hole of the double-effect separator (15-1), an outlet of the double-effect circulating pump (15-3) is respectively connected with a feed hole of the double-effect heater (15-2) and a front pipeline (14-5) of the single-effect circulating pump through branch pipelines, and a discharge hole of the double-effect heater (15-2) is connected with a feed hole of the double-effect separator (15-1) through a pipeline; two ends of a front pipeline (14-5) of the first-effect circulating pump are respectively connected with an inlet of the first-effect circulating pump (14-3) and a discharge hole of the first-effect separator (14-1), an outlet of the first-effect circulating pump (14-3) is connected to a feed hole of the first-effect heater (14-2) through a pipeline, and a discharge hole of the first-effect heater (14-2) is connected to a feed hole of the first-effect separator (14-1) through a pipeline; the discharge hole of the one-effect separator (14-1) is connected to a titanium hydroxide discharge pump (16) through a pipeline;

a steam inlet of a shell pass of the first-effect heater (14-2) is connected with a raw steam inlet pipeline (21), a condensate outlet of the shell pass of the first-effect heater is connected to a condensate inlet of a raw steam condensate water tank (14-4) through a pipeline, a condensate outlet of the raw steam condensate water tank (14-4) is connected with an inlet of a raw steam condensate water pump (17) through a pipeline, and an outlet of the raw steam condensate water pump (17) is connected to a second-stage preheater (13) through a pipeline;

a secondary steam outlet at the top of the primary-effect separator (14-1) is connected to a steam inlet of a shell pass of the secondary-effect heater (15-2) through a pipeline, and a condensate outlet of the shell pass of the secondary-effect heater (15-2) is connected to a secondary steam condensate water tank (15-4) through a pipeline; a steam outlet at the top of the secondary steam condenser (15-1) is connected to a gas inlet of a shell pass of the secondary steam condenser (15-6) through a pipeline, a non-condensable gas outlet of the shell pass of the primary heater (14-2) and a non-condensable gas outlet of the shell pass of the secondary heater (15-2) are connected to a gas inlet of the shell pass of the secondary steam condenser (15-6) through pipelines, a condensate outlet of the shell pass of the secondary steam condenser (15-6) is connected to a secondary steam condensate water tank (15-4) through a pipeline, a condensate outlet of the secondary steam condensate water tank (15-4) is connected to an inlet of a secondary steam condensate water pump (18) through a pipeline, and an outlet of the secondary steam condensate water pump (18) is connected to the primary preheater (12) through a pipeline; the non-condensable gas outlet of the secondary steam condensate water tank (15-4) is connected to a non-condensable gas vacuum pump (19) through a pipeline.

6. The apparatus for recovering titanium and simultaneously extracting ammonium chloride from acid sludge in olefin polymerization industry according to claim 1, wherein: the hydrochloric acid neutralization system comprises a neutralization device (25-1), an acid adjusting box (25-2), a hydrochloric acid storage tank (25-3) and a hydrochloric acid dosing pump (25-4), wherein the neutralization device (25-1) is provided with a liquid inlet pipeline and a liquid outlet pipeline, a liquid outlet of the hydrochloric acid storage tank (25-3) is connected with a liquid inlet of the hydrochloric acid dosing pump (25-4), a liquid outlet of the hydrochloric acid dosing pump (25-4) is connected with the liquid inlet pipeline of the neutralization device (25-1) through a pipeline, and a liquid outlet pipeline of the neutralization device (25-1) is connected with the acid adjusting box (25-2); the liquid outlet pipeline of the neutralization device (25-1) is connected with a PH detection device.

7. The apparatus for recovering titanium and simultaneously extracting ammonium chloride from acid sludge in olefin polymerization industry according to claim 1, wherein: the ammonium chloride electrodialysis membrane concentration system comprises an electrodialysis circulating device, a concentrated water output device and a fresh water reverse osmosis membrane desalination device; the electrodialysis circulating device comprises an electrodialysis desalting solution tank (26-1), an electrodialysis desalting circulating pump (26-2), an electrodialyzer (26-3), an electrodialysis concentrated solution circulating pump (26-4) and an electrodialysis concentrated solution tank (26-5); a liquid outlet of the acid adjusting box (25-2) is connected to a liquid inlet of the electrodialysis desalination liquid box (26-1), a liquid outlet of the electrodialysis desalination liquid box (26-1) is connected to a liquid inlet of the electrodialysis desalination circulating pump (26-2), a liquid outlet of the electrodialysis desalination circulating pump (26-2) is connected to a fresh water side liquid inlet end of the electrodialyzer (26-3) through a pipeline, and a fresh water side liquid outlet end of the electrodialyzer (26-3) is connected to the electrodialysis desalination liquid box (26-1) through a pipeline; one liquid outlet of the electrodialysis concentrated solution tank (26-5) is connected to the liquid inlet end of an electrodialysis concentrated solution circulating pump (26-4), the liquid outlet end of the electrodialysis concentrated solution circulating pump (26-4) is connected to the liquid inlet end of the concentrated water side of the electrodialyzer (26-3) through a pipeline, and the liquid outlet end of the concentrated water side of the electrodialyzer (26-3) is connected to the liquid inlet of the electrodialysis concentrated solution tank (26-5) through a pipeline; the other liquid outlet of the electrodialysis concentrated solution box (26-5) is connected with a concentrated water output device, and the concentrated water output device is connected with an evaporative crystallization system; the upper part of the electrodialysis desalination liquid tank (26-1) is provided with an overflow port, and the overflow port is connected to a fresh water reverse osmosis membrane desalination device through a pipeline; the concentrated water end of the fresh water reverse osmosis membrane desalination device is connected back to a tubular membrane water production tank of a tubular ultrafiltration membrane concentration system through a pipeline or directly connected back to an electrodialysis desalination tank; the fresh water end of the fresh water reverse osmosis membrane desalination device is connected with a discharge pipeline and is connected to the normal temperature and normal pressure hydrolysis system.