CN1082004A

CN1082004A - Produce a kind of efficient process of ventilation breather or cupric oxide

Info

Publication number: CN1082004A
Application number: CN 92109468
Authority: CN
Inventors: 王水平
Original assignee: COMPREHENSIVE SCIENCE AND TECHNOLOGY INST OF ENERGY HUANGSHI CITY
Current assignee: COMPREHENSIVE SCIENCE AND TECHNOLOGY INST OF ENERGY HUANGSHI CITY
Priority date: 1992-08-12
Filing date: 1992-08-12
Publication date: 1994-02-16

Abstract

A kind of efficient process of synchronous production ventilation breather or cupric oxide, in the leaching building-up reactions, be that the copper material is added in the ammonium bicarbonate soln, temperature of reaction is 50 ℃-70 ℃, and in the reaction whole process, add ammonia or ammoniacal liquor continuously or intermittently, forced air in the reaction, only need the above minute-pressure of 1.2 standard atmospheric pressures, in thermolysis, removed simultaneously the carbonic acid gas dose, take whole process normal pressure or minute-pressure can get cupric oxide reagent or take early stage normal pressure or minute-pressure to decompose, later stage negative pressure decomposition then gets ventilation breather, and thermolysis terminal point pH gets 7-8.The present invention is 60%～80% of an old technology cost, constant product quality, and the purity height, easy to operate, have stronger practicality and remarkable economic efficiency.

Description

Produce a kind of efficient process of ventilation breather or cupric oxide

The present invention relates to the Chemical Manufacture Application Areas.

At present, the method that ventilation breather is produced in common employing is a copper sulfate method, be that copper-bath is after impurity elimination is handled, add sodium bicarbonate precipitation, filtration, thermolysis, refilter, dry, dry, pack product, this processing method comparative maturity with deionized water or distilled water wash, quality product is also more stable, but the technological process of production is long, the production cost height, and the product deironing comparatively bothers.

Reported the production technique of ammonia process production ventilation breather according to pertinent data, also be written into " inorganic chemicals industry " book (the P333 page or leaf is published by Chemical Industry Press), but because this technology only is confined to small-scale test, do not see industrialness manufacturer as yet, this technology wants strictness to follow Cu+(NH ₄) ₂CO ₃+ 2NH ^[o] ₃→ Cu(NH ₃) ₄CO ₃This composition principle carries out, and because of the easy volatile of free ammonia, limited to the temperature of building-up reactions, it is very difficult to want to improve speed of response like this, and under room temperature (25 ℃), the copper material reaction times that wants to dissolve larger particles is very long, thus the source of having limited the copper material, moreover, and the whole compound quite stable of the part of the cuprammonium that forms, the heat energy that corresponding thermolysis needs is big, the resolving time is long, thereby has caused the hydrolysis of ventilation breather to be quickened, and is difficult to obtain the ventilation breather monomer.In order to address this problem, former lab scale has adopted thermolysis to add CO simultaneously ₂The hydrolysis (its principle is as follows) that suppresses ventilation breather can guarantee quality product.

For all the foregoing reasons, though the ammonia process production technique is more advanced, because the ammonia consumption is bigger, and dry ice (CO ₂) expense of raw materials is higher, with the both economical benefit of copper sulfate method be not fairly obvious, and in building-up process, do not have suitable detection means, production technique is difficult to control, this is this technology major cause of once using of end at home.

The production technique of existing cupric oxide then is that the ventilation breather after aforesaid method is purified carries out roasting, pulverizing and gets.

The object of the present invention is to provide that a kind of production cost is low, the processing method of remarkable in economical benefits, constant product quality, purity height, easy-operating production ventilation breather, this method again can the direct production cupric oxide simultaneously.

Concrete processing method of the present invention is:

1. leaching building-up reactions, be that the copper material is once added (being carbonic acid ammonia solution normal-temperature reaction originally) in the ammonium bicarbonate solution, temperature of reaction is 50 ℃～70 ℃, and change once is incorporated as continuous adding or intermittently adds and equimolar ammonia of ammonium hydrogencarbonate or ammoniacal liquor in reacting whole process, and the normal atmosphere of forced air change more than 7 in the reaction is the minute-pressures more than 1.2 standard atmospheric pressures; Reaction formula is:

2. filter: take usual way to get final product.

3. thermolysis: feeding the steam heating temperature is 80 ℃～100 ℃, remove the dioxy part carbon dose of former technology, take whole process normal pressure or minute-pressure to decompose and promptly get cupric oxide, or take two to go on foot decomposition: be normal pressure or minute-pressure decomposition (1-2 standard atmospheric pressure) early stage, the later stage is that the negative pressure decomposition of 0-0.8 standard atmospheric pressure then gets ventilation breather.Pyrolysated terminal point pH value is 7-8, dries, dries, chemically examines, sieves, packs product through 5 common process filtrations, washings then.

Ammonia solution normal temperature (25 ℃) leaching that becomes orthocarbonic acid ammonia in the present invention is that single carbonic acid ammonia solution leaches for the ammonia solution (50 ℃～70 ℃) of equimolar ammonium hydrogencarbonate, thereby adjusted the ratio of carbon and ammonia, (become four parts and be two parts) can suppress the hydrolysis of ventilation breather in the thermal decomposition process; A proportioning that becomes the ammonia solution of orthocarbonic acid ammonia again is incorporated as and once adds ammonium hydrogencarbonate, continuous again or intermittent injecting NH ₃, avoided the volatilization of a large amount of free ammonias, the pressure of forced air reduces greatly simultaneously.Therefore, technical process of the present invention is shortened, and consumes and reduces, thereby cost is reduced greatly, has remarkable economic efficiency, facts have proved, use the constant product quality that the present invention produces, the purity height has very big using value.

The invention will be further described below in conjunction with accompanying drawing:

Accompanying drawing is a process flow sheet of the present invention.

Embodiment 1: as follows referring to accompanying drawing, technical process of the present invention:

Quantitative or excessive adding copper material adds pure water or mother liquor water constant volume in retort, the ammonium hydrogencarbonate dissolving that adds 2m then, slowly add and the equimolar ammoniacal liquor of ammonium hydrogencarbonate, continuous 1.2 atmospheric pneumatic blending of feeding (air flow quantity is more than 5 times of actual oxygen-consumption) are kept temperature of reaction, and (general using thermolysis waste heat all can at 50 ℃, feed steam-heated cal(l)andria in case of necessity), meet sulfuric acid test (promptly reacting) to reaction solution.

Sulfuric acid test is: get the about 5ml of clear liquid, add sulphate reagent and must not produce red precipitate.

Detect principle:

Blue look solution illustrates and reacts.

The building-up reactions principle:

Two. filter: will react filtrate, and put into the filtration basin natural filtration that is lined with 747 filter clothes, filtrate should be limpid transparent, and filtrate collection is to basin.

Three, thermolysis: will filter good filtrate and put into the thermolysis jar and be settled to scale, feed open steam heating (vapor pressure is 1.5 normal atmosphere), when treating that feed temperature rises to 60 ℃, open the recirculated water cooling and reclaim ammoniacal liquor, continue to treat thermolysis mother [Cu more than the logical steam-heated cal(l)andria to 80 ℃ ²⁺] reduce to 15g/l when following (pH value general 10), carry out negative pressure ammonia still process, pressure-controlling gets final product at 0.5 normal atmosphere, treats that thermolysis mother liquor PH filtered by 8 o'clock promptly to get ventilation breather:

Four, washing: the wet product that will filter after doing get final product with low chlorine or the washing of dechlorination tap water, also available distilled water, and deionized water washs, and dries then to sample is chloride to be lower than standard.

Five, oven dry;

Six, check: the technical indicator that obtains product

Seven, sieve: general granularity is 300 orders.

Eight, packing is produced.

Embodiment 2: the main technique method is with example 1, and wherein, the first step temperature of reaction is 60 ℃, and pressurized air pressure is 1.5 normal atmosphere; The logical vapour heating and temperature control of the thermolysis in the 3rd step is at 100 ℃.Normal pressure decomposition nut liquid PH can directly obtain cupric oxide by 7 o'clock.

Carry out the back step equally and wash, dry, sieve, check, pack product.

Embodiment 3: the main technique method is with example 1, and wherein, the temperature of reaction of the first step is 70 ℃, and pressurized air pressure is 1.5 normal atmosphere, and the thermolysis Heating temperature in the 3rd step is 90 ℃, and logical steam pressure is 2 normal atmosphere, treats thermolysis mother liquor [Cu ²⁺] reduce to 15g/l when following, carry out negative pressure (being controlled at 0-0.8 normal atmosphere) ammonia still process, treat thermolysis mother liquor PH by 7.5 o'clock, filter the wet product of basic carbonate hydrogen ammonia, then through washing, dry, sieve, check, pack product.

Claims

Produce a kind of efficient process of ventilation breather or cupric oxide, include leaching building-up reactions, filtration, thermolysis, filtration, washing and dries, dry, chemically examine, sieve, pack eight main technique steps of product, it is characterized in that:

In a, the leaching building-up reactions, be once to join the copper material in the ammonium bicarbonate solution, temperature of reaction is 50 ℃～70 ℃, and in the reaction whole process, add continuously or intermittently add and equimolar ammoniacal liquor of ammonium hydrogencarbonate or ammonia, forced air in the reaction is that the above minute-pressure of 1.2 standard atmospheric pressures gets final product, and reaction formula is Cu+NH ₄HCO ₃+ NH ₃+ 1/2 O ₂=Cu (NH ₃) ₂CO ₃

Adding the steam heating temperature in b, the thermolysis is 80 ℃～100 ℃, remove the carbonic acid gas dose of former technology, take whole process normal pressure or minute-pressure branch to solve cupric oxide, or taked for two steps decomposed: decompose later stage for normal pressure or minute-pressure early stage is that the negative pressure of 0～0.8 big standard atmospheric pressure is decomposed and then got ventilation breather; Thermolysis terminal point PH gets 7～8.