CN216106008U - Recovery processing device of glass sculpture waste liquid - Google Patents

Abstract

The utility model discloses a recovery processing device of glass etching waste liquid, which comprises a defluorination reaction kettle, a condenser and a hydrofluoric acid storage tank which are connected in sequence, a three-stage falling film water absorption system connected with a gas output port of the condenser, a neutralization kettle connected with a liquid outlet of the defluorination reaction kettle, a crystallization kettle connected with a discharge valve of the neutralization kettle and a controller. According to the utility model, the defluorination reaction kettle and the falling film absorption system are adopted to recover hydrofluoric acid in the glass etching waste liquid, and the residual waste liquid is neutralized and crystallized to obtain nitrogenous salt which can be used as a composite nitrogen fertilizer byproduct for sale, so that the problems of environmental pollution and waste of the glass etching waste liquid are well solved, the purpose of clean production of enterprises is achieved, the generation of three wastes is reduced, the effect of circular economy is achieved, and an energy-saving and environment-friendly production support is created for the enterprises.

Description

Recovery processing device of glass sculpture waste liquid

Technical Field

The utility model relates to the technical field of industrial waste liquid recovery, in particular to a recovery processing device for glass etching waste liquid.

Background

Due to the fine extension of the glass industry, glass is required to be deeply processed in the life of various glass artware. The methods for thinning and surface treatment of glass mainly comprise physical tempering, chemical tempering, acid treatment enhancement and the like. The surface treatment method is acid treatment, and etching thinning treatment using hydrofluoric acid as a main component is commonly used at present. The content of HF in the glass etching thinning liquid is continuously reduced in the using process, and H is₂SiF₆Gradually accumulate when a certain concentration is reached (H)₂SiF₆The content is 10-15%), the viscosity of the system is obviously increased, and the change of the etching rate is large, so that the glass surface treatment effect is greatly influenced. At this time, the etching solution must be replaced. The waste liquid after etching and thinning treatment mainly contains fluorosilicate (SiF)₆ ^-) Nitrate radical (NO)₃ ^-) Ammonium heel (NH)₄ ⁺) Fluorine ion (F)^-) And hydrogen ion (H)⁺) And the like, wherein the contents of the components are respectively as follows: f^-：150～200g/L，SiF₆ ^-：100～150g/L，NO₃ ^-：80～120g/L，NH₄ ⁺：80～120g/L。

At present, the method generally adopted by the fluorine-containing acidic waste liquid generated by glass etching and thinning in the industry is a lime or calcium chloride neutralization treatment method. Mainly uses excessive lime or calcium chloride and H in etching liquid⁺、F^-And H₂SiF₆And (3) carrying out an equal reaction to neutralize the acid component in the waste acid, and reacting F^-Conversion to CaF₂Precipitation of H₂SiF₆Conversion to CaSiF₆Precipitation, by which the acid content and F in the fluorine-containing waste liquid can be made^-And SiF₆ ^-The content of the substances reaches the standard and is discharged, but a great amount of CaF is generated₂、CaSiF₆The solid wastes are mixed and treated specially as dangerous wastes in China, so that the treatment cost is high, the production cost of enterprises is increased, and the burden of the enterprises is increased; in addition, because of different formulations of the etching agent, NO is often contained in the wastewater₃ ^-、NH₄ ⁺And water-soluble substances are difficult to remove, the treated water quality cannot reach the standard and is discharged, and the concept of clean production, resource recycling and environmental protection is not met.

SUMMERY OF THE UTILITY MODEL

The utility model aims to solve the technical problem of providing a device for recovering and treating glass etching waste liquid, which is used for recovering hydrofluoric acid in the glass etching waste liquid and extracting a composite nitrogen fertilizer byproduct from the residual waste liquid, thereby better solving the problems of environmental pollution and waste of the glass etching waste liquid.

The technical scheme of the utility model is as follows:

the utility model provides a recovery processing device of glass sculpture waste liquid, is including defluorination reation kettle, condenser and the hydrofluoric acid storage tank that connects in order, the tertiary falling liquid film water absorption system who is connected with condenser gas outlet, the neutralization kettle who is connected with defluorination reation kettle leakage fluid dram, the crystallization kettle and the controller that are connected with neutralization kettle relief valve, the liquid outlet of crystallization kettle be connected with the feed inlet of neutralization kettle, defluorination reation kettle's inlet pipe on be connected with the sulfuric acid tank, be provided with the pH sensor in the defluorination reation kettle, sulfuric acid tank advance acid valve, pH sensor, defluorination reation kettle, condenser, tertiary falling film water absorption system, neutralization kettle, crystallization kettle all be connected with the controller.

And a steam outlet of the neutralization kettle is connected with an inlet of a recovery condenser, and an outlet of the recovery condenser is connected with a circulating water tank. The utility model has the advantages that:

according to the utility model, the defluorination reaction kettle and the falling film absorption system are adopted to recover hydrofluoric acid in the glass etching waste liquid, and the residual waste liquid is neutralized and crystallized to obtain nitrogenous salt which can be used as a composite nitrogen fertilizer byproduct for sale, so that the problems of environmental pollution and waste of the glass etching waste liquid are well solved, the purpose of clean production of enterprises is achieved, the generation of three wastes is reduced, the effect of circular economy is achieved, and an energy-saving and environment-friendly production support is created for the enterprises.

Drawings

Fig. 1 is a schematic structural view of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

See fig. 1, a recovery processing device of glass etching waste liquid, including the defluorination reaction of connecting in order, 1, condenser 3 and hydrofluoric acid storage tank 4, the tertiary falling film water absorption system (one-level falling film absorption tower 5, second grade falling film absorption tower 6 and tertiary falling film absorption tower 7) that is connected with condenser 3 gas outlet, neutralization kettle 8 that is connected with defluorination reation kettle 1 drain outlet, crystallization kettle 9 that is connected with neutralization kettle 8 blow-off valve, and a controller, crystallization kettle 9's liquid outlet is connected with neutralization kettle 8's feed inlet, be connected with sulfuric acid tank 2 on defluorination reation kettle 1's the inlet pipe, be provided with the pH sensor in the defluorination reation kettle 1, sulfuric acid tank 2's acid inlet valve, the pH sensor, defluorination reation kettle 1, condenser 3, tertiary falling film water absorption system, neutralization kettle 8, crystallization kettle 9 all is connected with the controller.

Wherein, the steam outlet of the neutralization kettle 8 is connected with the inlet of a recovery condenser 10, and the outlet of the recovery condenser 10 is connected with a circulating water tank 11.

A recovery processing method of glass etching waste liquid specifically comprises the following steps:

(1) adjusting the pH value: putting the glass etching waste liquid into a defluorination reaction kettle 1, wherein the main component of the glass etching waste liquid is fluosilicate 95 g/L; 158g/L of fluoride ions; 190g/L of ammonium radical and 98g/L of nitrate radical; adding sulfuric acid (with the mass concentration of 30%) into the glass etching waste liquid to adjust the pH value to be less than 1, so that all fluorine elements in the glass etching waste liquid are converted into fluorine ions;

(2) dehydrofluorination: under the conditions of stirring and heating, introducing nitrogen into the defluorination reaction kettle 1, and controlling the temperature at 80 ℃, thereby removing an azeotrope of hydrogen fluoride and water from the glass etching waste liquid;

(3) and condensation: after an azeotrope of hydrogen fluoride and water is condensed by a condenser 3, a hydrofluoric acid solution is obtained and stored in a hydrofluoric acid storage tank 4;

(4) falling film absorption: hydrogen fluoride tail gas which is not condensed and recycled from the condenser 3 enters a three-stage falling film water absorption system, water is used as an absorbent, and the hydrogen fluoride tail gas is circularly absorbed into saturated solution through three-stage falling film absorption and then is stored for later use; the three-level falling film water absorption system comprises a first-level falling film absorption tower 5, a second-level falling film absorption tower 6 and a third-level falling film absorption tower 7, the three-level falling film water absorption system takes water as an absorbent, a first-level falling film absorption circulating pump P2, a second-level falling film absorption circulating pump P3 and a third-level falling film absorption circulating pump P4 are started to circularly absorb the water, after the first-level falling film is circularly absorbed into a saturated solution, the saturated solution is stored and reserved, tap water is pumped into the saturated solution by opening a valve of the three-level falling film absorption tower 7, and the top of the three-level falling film absorption tower 7 is emptied after reaching the standard;

(5) and neutralizing: pumping the residual waste liquid in the defluorination reaction kettle 1 into a neutralization kettle 8 through a waste liquid conveying pump P1, analyzing and detecting that the fluorine content in the mixed liquid after defluorination is 8.3g/L and the defluorination rate is about 96%, and then adding potassium carbonate into the neutralization kettle 8 for neutralization reaction to ensure that the pH value of the waste water is neutral and is between 7 and 8;

(6) and (3) distillation: heating and distilling the water in the mixed solution after the neutralization reaction in the neutralization kettle 8 in a negative pressure state to improve the concentration of the mixed solution to 61%, condensing the distilled water by a recovery condenser 10 and then feeding the condensed water into a circulating water tank 11, wherein the circulating water tank also plays a role in absorbing tail gas hydrogen fluoride to ensure that the gas is discharged after reaching the standard;

(7) and crystallizing: the mixed liquid after distillation and dehydration is discharged into a crystallization kettle 9, after cooling and crystallization, the crystallized solid is taken as a composite nitrogen fertilizer by-product, and the crystallized waste liquid is returned to a neutralization kettle 8 again for distillation.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the utility model, the scope of which is defined in the appended claims and their equivalents.

Claims (2)

1. The utility model provides a recovery processing device of glass sculpture waste liquid which characterized in that: including defluorination reation kettle, condenser and the hydrofluoric acid storage tank connected in order, the tertiary falling liquid film water absorption system who is connected with condenser gas outlet, with the neutralization cauldron that defluorination reation kettle leakage fluid dram is connected, with crystallization kettle and the controller that neutralization cauldron bleeder valve is connected, crystallization kettle's liquid outlet be connected with the feed inlet of neutralization cauldron, defluorination reation kettle's inlet pipe on be connected with the sulfuric acid tank, be provided with the pH sensor in the defluorination reation kettle, sulfuric acid tank advance acid valve, pH sensor, defluorination reation kettle, condenser, tertiary falling film water absorption system, neutralization cauldron, crystallization kettle all be connected with the controller.

2. The recycling apparatus according to claim 1, wherein: and a steam outlet of the neutralization kettle is connected with an inlet of a recovery condenser, and an outlet of the recovery condenser is connected with a circulating water tank.

Images