CN104163514A

CN104163514A - Process for preparing ammonium water and hydrochloric acid from ammonium chloride wastewater with zero emission

Info

Publication number: CN104163514A
Application number: CN201410403821.XA
Authority: CN
Inventors: 孙洪贵; 王威; 李振峰; 陈世郁
Original assignee: XIAMEN STARMEM FILM TECHNOLOGY Co Ltd
Current assignee: XIAMEN STARMEM FILM TECHNOLOGY Co Ltd
Priority date: 2014-08-16
Filing date: 2014-08-16
Publication date: 2014-11-26
Anticipated expiration: 2034-08-16
Also published as: CN104163514B

Abstract

The invention discloses a process for preparing ammonium water and hydrochloric acid from ammonium chloride wastewater with zero emission. The process comprises the following steps: S1, collecting ammonium chloride wastewater in an adjusting pond, and filtering the ammonium chloride wastewater in the adjusting pond by use of a micro-filtration membrane to obtain a micro-filtration dialysate and a micro-filtration concentrated solution, wherein the micro-filtration concentrated solution returns to the adjusting pond for circular treatment; S2, carrying out high-pressure reverse osmosis separation on the micro-filtration dialysate to obtain high-pressure reverse osmosis dialysate and a high-pressure reverse osmosis concentrated solution; S3, feeding the high-pressure reverse osmosis concentrated solution into a bipolar membrane for treatment to obtain hydrochloric acid and ammonium water; and S4, carrying out low-temperature reverse osmosis separation on the high-pressure reverse osmosis dialysate to obtain low-temperature reverse osmosis dialysate and a low-temperature reverse osmosis concentrated solution, wherein the low-temperature reverse osmosis concentrated solution enters into high-pressure reverse osmosis for circular treatment and the low-temperature reverse osmosis dialysate returns for production. The process disclosed by the invention can be used for avoiding high cost caused by evaporation, so that salt and moisture in wastewater can be recycled in the process, and zero emission of the wastewater is achieved.

Description

A kind of ammonium chloride waste-water ammoniacal liquor processed, hydrochloric acid technique of zero discharge

Technical field

The present invention relates to hydrometallurgy field, particularly a kind of ammonium chloride waste-water ammoniacal liquor processed, hydrochloric acid zero release novel process.

Background technology

One of strategic mineral resources that the Gu Shi world is important, it has the features such as high temperature resistant, corrosion-resistant, high strength and ferromagnetism, be widely used in Aeronautics and Astronautics, electrical equipment, machinofacture, Wimet, magneticsubstance, chemistry and the industry such as ceramic, in national economy and social development, acquire a special sense.At present cobalt chloride synthetic mostly is cobalt ore after pre-treatment and synthesizes under the catalysts such as nitric acid with hydrochloric acid, owing to containing the impurity such as nickel, iron, zinc, lead in cobalt ore, unavoidably need to add ammoniacal liquor, hydrogen peroxide to remove.Therefore in filtrate, contain ammonium sulfate after filtration.

Hydrometallurgy mainly comprises, as shown in Figure 1: ammonium chloride waste-water in processing, because ion content is high, and the problem such as ammonium chloride low finished product cost, directly outer row.The general methods such as multiple-effect evaporation that adopt are processed, and cause evaporation cost high, reclaim meaning lower, are difficult points on ammonium chloride waste-water is processed always.

Summary of the invention

For deficiency of the prior art, the object of the present invention is to provide the one can efficient recovery water resources, reclaim salinity and reduce enterprise's production cost, improve ammonium chloride waste-water ammoniacal liquor processed, the hydrochloric acid technique of zero discharge of income water cycle reuse.

For achieving the above object, the technical scheme that the present invention proposes is: a kind of ammonium chloride waste-water ammoniacal liquor processed, hydrochloric acid technique of zero discharge, it is characterized in that, and comprise the steps:

Step 1: ammonium chloride waste-water is collected in equalizing tank, the ammonium chloride waste-water in equalizing tank carries out micro-filtrate membrane filtration, obtains micro-filtration dialyzate and micro-filtration concentrated solution, and micro-filtration concentrated solution is back to equalizing tank circular treatment;

Step 2: micro-filtration dialyzate carries out high pressure reverse osmosis isolation, obtains high pressure reverse osmosis dialyzate and high pressure reverse osmosis concentrated liquid;

Step 3: high pressure reverse osmosis concentrated liquid enters in Bipolar Membrane system and enters the processing of Bipolar Membrane system, obtains hydrochloric acid and ammoniacal liquor;

Step 4: high pressure reverse osmosis dialyzate carries out low pressure reverse osmosis separation, obtains low pressure reverse osmosis dialyzate and low pressure reverse osmosis concentrated solution, and low pressure reverse osmosis concentrated solution enters circular treatment in high pressure reverse osmosis, and low pressure reverse osmosis dialyzate is back to production.

Preferably, the Bipolar Membrane in described Bipolar Membrane system is polyether-ether-ketone material, and service temperature, below 300 DEG C, selects perviousness more than 96%.

Preferably, in described Bipolar Membrane system, use titanium platinum plating as anodic-cathodic, diaphragm is homogeneous membrane, and control voltage is 20V, and Yu Suan chamber, feed liquid chamber, alkali chamber volume ratio are 1:5.

Preferably, the factory effluent of described ammonium chloride waste-water for producing in cobalt chloride smelting industry.

Adopt technique scheme, ammonium chloride waste-water of the present invention ammoniacal liquor processed, hydrochloric acid technique of zero discharge, will concentrate afterwards feed liquid by Bipolar Membrane and make hydrochloric acid and ammoniacal liquor reuse to technique, by low pressure reverse osmosis system, the advanced treatment of product water be obtained to reuse water; The innovative point of whole technique is to make ammonium chloride waste-water to reach the object of reuse, abandons the great number cost that evaporation brings, and salt and moisture in waste water can be recycled in technique, and reach the zero release of waste water.

Brief description of the drawings

Fig. 1 is hydrometallurgical processes schema;

Fig. 2 is ammonium chloride waste-water of the present invention ammoniacal liquor processed, hydrochloric acid technique of zero discharge schema.

Embodiment

Below in conjunction with the drawings and specific embodiments, the present invention will be further described.

Embodiment:

The factory effluent of waste water for producing in cobalt chloride smelting industry that the present embodiment uses, concrete technology flow process as shown in Figure 2:

Step 1: use microfiltration systems to process ammonium chloride waste-water, remove suspended substance, floss and particle in feed liquid, ensure the steady running of follow-up reverse osmosis, the dense circulation of micro-filtration concentrates, and carries out three batches of experiments:

From experimental data, pressure that microfiltration systems has, high yield water rate, etc. feature, flux has all reached very high level when processing feed liquid simultaneously, cost of investment is also relatively low.

Step 2: use high pressure reverse osmosis to process micro-filtration dialyzate, micro-filtration dialyzate contains a large amount of chlorions, ammonium ion and a small amount of cobalt ion; General chlorion >25g/L, ammonium ion >10g/L, cobalt ion <0.04g/L, control temperature at 40 DEG C, pressure 60Bar; Carry out three batches of experiments:

From experimental data, by high pressure reverse osmosis, feed liquid intermediate ion is concentrated, there is cycles of concentration, producing water ratio compared with high.

Step 3: use Bipolar Membrane system to process high pressure reverse osmosis concentrated liquid, use titanium platinum plating as anodic-cathodic, use diaphragm to be homogeneous membrane, control voltage is 20V, and Yu Suan chamber, feed liquid chamber, alkali chamber volume ratio are 1:5, carry out three batches of experiments:

From experimental data, use homogeneous membrane as diaphragm, titanium platinum plating has the features such as current efficiency is high, energy consumption is lower as pole plate when the handle high voltages reverse osmosis concentrated liquid, and product acid, alkali can directly return in former technique and use.

Step 4: use low pressure reverse osmosis system to process electric osmose high pressure reverse osmosis dialyzate, make dialyzate directly carry out reuse, reach the zero release of ammonium chloride waste-water, controlling into film pressure is 20Bar, and temperature, below 40 DEG C, is carried out three batches of experiments:

From experimental data, the reverse osmosis system features such as tool producing water ratio is high in the time of handle high voltages reverse osmosis dialyzate, average flux is high, cost of investment is lower, and product water reaches reuse rank completely.

In the above-described embodiments, only the present invention has been carried out to exemplary description, but those skilled in the art are reading after present patent application and can carry out various amendments to the present invention without departing from the spirit and scope of the present invention.

Claims

1. ammonium chloride waste-water ammoniacal liquor processed, a hydrochloric acid technique of zero discharge, is characterized in that, comprises the steps:

2. a kind of ammonium chloride waste-water according to claim 1 ammoniacal liquor processed, hydrochloric acid technique of zero discharge, is characterized in that, the Bipolar Membrane in described Bipolar Membrane system is polyether-ether-ketone material, and service temperature, below 300 DEG C, selects perviousness more than 96%.

3. a kind of ammonium chloride waste-water according to claim 1 ammoniacal liquor processed, hydrochloric acid technique of zero discharge, it is characterized in that, in described Bipolar Membrane system, use titanium platinum plating as anodic-cathodic, diaphragm is homogeneous membrane, control voltage is 20V, and Yu Suan chamber, feed liquid chamber, alkali chamber volume ratio are 1:5.

4. a kind of ammonium chloride waste-water according to claim 1 ammoniacal liquor processed, hydrochloric acid technique of zero discharge, is characterized in that, the factory effluent of described ammonium chloride waste-water for producing in cobalt chloride smelting industry.