CN1054956A

CN1054956A - A kind of method of producing Red copper oxide

Info

Publication number: CN1054956A
Application number: CN 90105244
Authority: CN
Inventors: 刘登良
Original assignee: GUXIAN CHEMICAL PLANT YANTAI CITY
Current assignee: GUXIAN CHEMICAL PLANT YANTAI CITY
Priority date: 1990-03-12
Filing date: 1990-03-12
Publication date: 1991-10-02
Anticipated expiration: 2005-03-12
Also published as: CN1027803C

Abstract

The invention belongs to the improvement of the method for producing Red copper oxide, it is characterized in that making CuSO as conditioning agent with inorganic salt ₄Be reduced into Cu2O, it has with short production cycle than present chemical industry dry method, wet method, and energy consumption is low, and the three wastes are few, the yield height, and the advantage that quality is high can be widely used in chemical industry and produce Red copper oxide.

Description

A kind of method of producing Red copper oxide

The invention belongs to the improvement of Red copper oxide production method.

At present, the method for the Red copper oxide of chemical industry production both at home and abroad is more, and is big to being divided into two kinds of dry method and wet methods.So-called dry method adopts CuSO exactly ₄The calcination method, its reaction process such as following mode journey are represented:

With the outstanding shortcoming of this method is cycle long (72hr), the equipment complexity, and the energy consumption height, serious three wastes, final product quality is poor, and yield is low.So-called wet method, existing multiple at present both at home and abroad, it has overcome the shortcoming of dry method to a certain extent, and attempting copper sulfate is example with the S-WAT reduction method directly, and its reaction process equation is as follows:

By aforesaid equation as can be seen: owing to generate a part Cu ₂O needs two molecule S-WATs, and although S-WAT serious offense amount in the reaction ratio of place is can recovery part SO ₂But Na ₂SO ₃Consume high.In addition, big excessive S-WAT exist and the strongly-acid of reaction medium can cause in the product free copper content increase low with once through yield, cost is high.Exemplify copper powder again and directly reduce copper sulfate method, according to Soviet Union's science and technology document announcement: at room temperature use thin copper powder (10um) directly to reduce copper sulfate and generate Red copper oxide, its reaction formula is as follows:

Entire reaction is carried out in acidic medium, because this reaction pair copper powder fineness requirement height, difficulty of processing is big, and long reaction time is so the industrialization feasibility is little.

Purpose of the present invention just provides a kind of novel method of producing Red copper oxide, and existing technical process is many, the cycle is long, energy consumption is high, the three wastes are many, yield is low to alleviate, of poor quality, weakness that cost is high.

Technical scheme of the present invention is achieved in that

A, batching: press NaCl, Na ₂SO ₃, Na ₂CO ₃With CuSO ₄5H ₂The molar ratio of O is: 0.3385～0.9302,0.5953～1.0417, and 0.2406～0.4333 gets raw material ready.

B, reduction: in enamel pot with CuSO ₄5H ₂O and NaCl are dissolved in water, and are heated to 40-70 ℃, are made into Na in another container ₂SO ₃And Na ₂CO ₃Mixed solution is added dropwise to this mixed solution in the enamel pot under agitation condition, is warming up to 90-100 ℃ then.

C, neutralization: 90-100 ℃ down in the enamel pot dropping concentration be 150g/l Na ₂CO ₃Solution is neutralized to till the pH value 4-7.

D, filtration, washing: neutralization finishes and keeps one hour after-filtration and wash to SO with 80 ℃ of washing water or alcohol ^2- ₄Ion is satisfied the criteria.

E, drying, packing: under vacuum condition, carry out drying under the 80-140 ℃ of temperature, packing makes finished product then.

The basic principles of chemistry of reduction process are in the technique scheme: CuSO ₄At Na ₂CO ₃Do under the conditioning agent condition and Na with NaCl ₂SO ₃Effect is reduced into CuCl, CuCl again with Na ₂SO ₃The NaOH effect that hydrolysis generates generates Cu ₂The O precipitation.Because entire reaction carries out under acidic conditions all the time, in and the time by adding Na ₂CO ₃Amount and speed adjust Na ₂SO ₃And NaHSO ₃Concentration form a buffer solution system, to keep metastable pH value environment, under suitable CuCl intermediate (the double salt form with NaCl is dissolved in the reaction system) is regulated, progressively and equably separate out red-purple Cu simultaneously ₂The O crystal.

Its reaction formula is as follows:

The present invention has comprehensively compared the whole bag of tricks that present home and abroad chemical industry is produced Red copper oxide, and as can be seen, the present invention has with short production cycle, and equipment is simple, less investment, energy consumption is low, the no three wastes, good work environment, labour intensity is low, yield height, the advantage that the product cost inferior quality is high.According to test product Cu ₂The O quality can reach U.S. ASTM standard.

Now with the present invention and dry production Cu ₂Each intermediate item contrast of O is listed as follows

Sequence number	Project name	Dry method	This law	Remarks
						1	Facility investment	260,000 yuan	80,000 yuan	100 tons/year
2	Production cycle	72hr	12hr
					3	Energy consumption	1000 yuan of/ton products	375 yuan of/ton products	Power cost
4	The three wastes	Dust and a large amount of water	Do not have
					5	Work situation	Dust	Do not have
6	Labour intensity	Manual work	Substantially there is not manual work
					7	Yield	About 90%	97－99％	Recycling Mother Solution
8	Cost	18.700 unit/ton product	17.771 unit/ton product
					9	Quality	Reach GB1620-79	Reach ASTM
10	Outward appearance	Garnet	Red-purple

Again the present invention is manufactured a finished product and dry production final product quality index is compared as follows:

GB standards project title	Index	Actual measurement	ASTM standards project title	Index	Actual measurement
						Total reducing power % 〉=	97	98	Total reducing power % 〉=	≥97	97.68
Total copper % 〉=	86	87	Total copper % 〉=	≥86	87.40
						Content % 〉=	95	95.75	Content % 〉=	≥97	97.21
Metallic copper %≤	2.0	1.0	Other metal %≤	≤0.5	0.5
						Vitriol (SO ₄ ^3-)％ ≤	0.3	0.1	Muriate (Cl ^－) and vitriol (SO ₄ ^3-) ％???????≤	≤0.5	0.44
Moisture content %≤	0.5	0.05	Acetone solution thing %≤	≤0.5	0.092
						Fineness (320 mesh sieve) %≤	0.5	0.1	Stability (falling) %≤	≤2.0	2.0
			Sieve thing (325 order) %≤	≤0.5	0.11
									Nitric acid insolubles %≤	≤0.1	0.0012

Accompanying drawing 1 is a process flow sheet of the present invention.

The present invention is further elaborated with embodiment below in conjunction with accompanying drawing 1:

Embodiment 1:

A, batching: the listed various composition quantity of according to the form below are got raw material ready

B, reduction: in enamel pot with CuSO ₄5H ₂O and NaCl are dissolved in water and are heated to 50 ℃; In another container, prepare Na ₂SO ₃And Na ₂CO ₃Mixed solution is added dropwise to mixed solution in the enamel pot under agitation condition, is warming up to 90 ℃ then.

C, neutralization: dripping concentration under 90 ℃ of conditions is 150g/1Na ₂CO ₃Solution is neutralized to PH4.1 to be ended.

D, filtration, washing: the neutralization insulation that finishes is filtered behind the 1hr, and washs to SO with 80 ℃ of washing water ^2- ₄Ion is satisfied the criteria.

E, drying: at vacuum high-temperature indoor (80-140 ℃) to filtering back gained Cu ₂The O crystal carries out drying, and packing makes finished product then.

Embodiment 2:

B, reduction: in enamel pot with CuSO ₄5H ₂O and NaCl are dissolved in water and are heated to 63 ℃; In another container, prepare Na ₂SO ₃And Na ₂CO ₃Mixed solution is added dropwise to mixed solution in the enamel pot under agitation condition, is warming up to 94 ℃ of neutralizations then, and dripping concentration under 94 ℃ of conditions is 150g/1Na ₂CO ₃Solution is neutralized to PH5.0 to be ended.

D, filtration, washing: the neutralization insulation that finishes is filtered behind the 1hr, and washs to SO with 75 ℃ of washing water ^2- ₄Ion is satisfied the criteria.

Claims

1, a kind of method of producing Red copper oxide is characterized in that making CuSO ₄5H ₂O is at Na ₂CO ₃Do under the condition of conditioning agent and Na with NaCl ₂SO ₃Effect is reduced into CuCl, CuCl again with Na ₂SO ₃The NaOH effect that hydrolysis generates generates Cu ₂The O precipitation is used Na ₂CO ₃In and after-filtration, again through the washing, drying makes finished product Cu ₂The O crystal.Its reaction formula is:

2, a kind of method of producing Red copper oxide according to claim 1 is characterized in that NaCl, Na ₂CO ₃, Na ₂SO ₃With CuSO ₄5H ₂The molar ratio scope of O add-on is respectively 0.3385～0.9302; 0.2406～0.4333; 0.5953～1.0417.

3, it is characterized in that according to claim 1 or 2 described a kind of methods of producing Red copper oxide reduction process is with CuSO ₄5H ₂After O and NaCl mixed solution are heated to 40-70 ℃, again with Na ₂SO ₃And Na ₂CO ₃Mixed solution drips under agitation condition, and reheat is to 90-100 ℃.

4, it is characterized in that using Na according to claim 1 or 2 described a kind of methods of producing Red copper oxide ₂CO ₃In and 90-100 ℃ of mixed solution till the pH value 4-7.

5, it is characterized in that using Na according to the described a kind of method of producing Red copper oxide of claim 3 ₂CO ₃In and 90-100 ℃ of mixed solution till the pH value 4-7.

6, according to claim 1 or 2 described a kind of methods of producing Red copper oxide, the mother liquor after it is characterized in that filtering, washing returns reduction process and reuses.

7, the mother liquor after it is characterized in that filtering, washing according to the described a kind of method of producing Red copper oxide of claim 3 returns reduction process and reuses.

8, the mother liquor after it is characterized in that filtering, washing according to the described a kind of method of producing Red copper oxide of claim 4 returns reduction process and reuses.