CN101559987A - Method for producing polyaluminum ferric chloride composite water purification agent by using plant slag and coal gangue - Google Patents

Abstract

The invention discloses a method for producing a polyaluminum ferric chloride composite water purification agent by using plant slag and coal gangue; the method features easily obtained raw materials and simple process, and reduces the pollution of the coal mines, electric power plants and other industries to the environment; the invention achieves multiple purposes. is a green process for producing polyaluminum chloride and has wild development prospect.

Description

The method of utilizing plant slag, coal gangue to produce polyaluminum ferric chloride composite water purification agent

Technical field

The present invention utilizes plant slag or coal gangue to produce polyaluminum ferric chloride composite water purification agent, especially utilizes solid waste-coal gangue of producing in coal mining, the dressing of coal by washing process a kind of water purification agent for main material production.This water purification agent is mainly used in the purifying treatment of process water, trade effluent, sanitary sewage etc.

Background technology

The composition of coal gangue is mainly inorganics, contain mineral compound and other trace elements such as a large amount of aluminium, iron, silicon, above-claimed cpd is the useful industrial raw material, as direct stacking, discarded, it will be a kind of significant wastage to resource, especially for the so comparatively deficient country of a resource of China, this waste more should be stopped.Measuring and calculating according to one's analysis, the coal gangue aluminum content that the Xie Zhuan mining area produces is about (in aluminum oxide) more than 22%, and iron-holder is about (in ferric oxide) more than 8%, and the aluminium in the above-mentioned waste residue, iron level are all quite considerable, have the actual recovered utility value.

Existing in the middle of the prior art utilizes flyash to produce the technology of water purification agent.Because flyash produces through high-temp combustion, wherein about 90% SiO ₂And Al ₂O ₃Be vitreous state, mainly with 3Al ₂O ₃SiO ₂The form of (andaluzite) exists, and not with active γ-Al ₂O ₃Form exist, therefore be difficult to directly be dissolved out with acid.Therefore open the Al-Si key of flyash, make A1 ₂O ₃Discharge in vitreum, there are a lot of problems in the preparation flocculation agent always.

Constantly perfect along with China's industrial expansion and environmental regulation, the treatment scale of waste water constantly increases, and the strength disposal of waste water also will constantly be strengthened.The raising of above-mentioned wastewater treatment level will drive the continuous development in Water Treatment Chemicals market, will roll up the demand of Water Treatment Chemicals.The method of domestic production aluminium iron polychloride (PAFC) has many, in the characteristics that oneself is respectively arranged aspect material choice, the production process route, at present mainly based in acid-soluble one-step, the acidleach and two-step approach, gel method, thermal decomposition method etc.; Raw material commonly used mainly contains: (1) pure aluminum (various aluminium processing fents such as aluminium ingot, aluminium ash, aluminium bits); (2) aluminum-containing mineral (as bauxite, clay, kaolin, alunite, coal gangue etc.); (3) aluminium salt compound (as aluminum chloride, Tai-Ace S 150 etc.); (4) flyash etc.China produces the mineral wealth that aluminium iron polychloride (PAFC) raw material that adopts is mainly development and use self with suiting measures to local conditions.The starting of China's aluminium iron polychloride production comes from the aluminium ash makes raw material.Because aluminium ash raw materials cost is cheap, production technique is terse, and its production technique the seventies is popularized rapidly in China.But the polymerize aluminum chloride product impurity that the aluminium ash is produced is more, is not used further to the purification of tap water after the eighties.The polymerize aluminum chloride product that early eighties, the raw materials for production of aluminium iron polychloride mainly adopt clay pit, kaolin ore and bauxite to produce, beyond the deironing, other index can reach external advanced level.Bauxite is the main raw material of ceramic industry and aluminium metallurgy, be the non-renewable Mineral resources of country, for the main material production aluminum chlorate of polymerized silicic acid needs ball milling and maturing process, needed for two steps synthetic with bauxite, production line is long, floor space is big, complex process, production cost height.

The main component of table 1 Xie Zhuan colliery coal gangue

Composition	SiO 3	Al 2O 3	Fe 2O 3	K 2O	S	TiO 2	MgO	CaO
									Content	59.82	22.16	8.22	3.87	1.33	1.29	1.25	1.24
Composition	BaO	Na 2O	MnO	P	V 2O 5	ZnO	Cr 2O 4
									Content	0.35	0.13	0.1	0.07	0.03	0.02	0.01

The main component of the bright plant slag in table 2 Xie Zhuan colliery

Composition	SiO 3	Al 2O 3	Fe 2O 3	CaO	SO 2	K 2O	MgO	TiO 2
									Content	50.70	30.30	6.43	4.5	2.56	2.01	1.32	1.24
Composition	Na 2O	Au	P	MnO	RhO	V 2O 5	CaO

Content

0.39

0.07

0.07

0.06

0.04

0.04

0.01

Summary of the invention

The object of the present invention is to provide a kind of method of utilizing plant slag, coal gangue production to produce polyaluminum ferric chloride composite water purification agent.This method not only raw material should get, and technology is simple, has reduced the pollution to environment of coal-mining industry and power station simultaneously, is to achieve many things at one stroke, and is the friendly process of producing polymerize aluminum chloride, and development prospect is very wide.

It comprises the steps:

Step 1 is pulverized: coal gangue or plant slag are crushed to below the particle diameter 8mm;

Step 2 acid in small, broken bits is molten: coal gangue after the roasting or spoil heat power plant pulverized slag are broken to about 60 orders, be that acid is molten continuously under 100～110 ℃ condition of normal pressure for 15%～20% hydrochloric acid with mass concentration, the molten equipment of acid adopts the still method, use the steam direct heating, stir with agitator in the molten process of acid, the reacting by heating time is 3～4 hours;

Step 3 concentrates polymerization: the molten mother liquor of acid is sent in the enamel still, under negative pressure state, concentrate with steam heating, when the mother liquor concentration and evaporation falls 45～50%, stop heating and concentrate, drop into a certain amount of calcium aluminate powder then, carry out polyreaction and basicity adjustment reaction, after 2～4 hours reaction times, carry out naturally cooling, be cooled to about 60 ℃, carry out squeeze and filter once more, the liquid of extrusion is the polymerize aluminum chloride iron product.Or the molten mother liquor of acid is directly imported polymerization adjust the pond and heat, dropping into a certain proportion of calcium aluminate powder then and carry out polymerization and basicity adjustment, resultant is the aluminium iron polychloride finished product;

The adjustment of step 4 concentration: the aluminium iron polychloride with previous step is produced, carry out the water distribution adjustment according to the concentration that records proportion and requirement, produce liquid and can sell.

Step 5 as production solid phase prod, the liquid that step 3 can be generated is through cylinder dried or adopt the aerosol desiccating method to produce, and promptly obtains solid polyaluminium chloride iron finished product.

The present invention is implemented, near but the coal gangue of piling up the mass consumption mining area not only, thereby discharge a large amount of soils, and the environmental ecology problem that slag dump manufactures also can be readily solved, simultaneously, owing to being the water purification agent low production cost of feedstock production, has the very strong market competitiveness with above-mentioned waste residue, estimate just can capture the mass market share at short notice, bring considerable economic will for project investment person.Spoil heat power plant slag main component and coal gangue are approaching, and coal gangue has obtained fully calcined in combustion processes, the activity of part aluminium sesquioxide is activated in the spoil, be very beneficial for separating out of aluminum oxide, highly beneficial to the rate of release that improves aluminium sesquioxide, and with the process that this kind raw material production can be removed the spoil calcining and activating from, can reduce production costs greatly, therefore utilize plant slag to produce aluminium iron polychloride and have good development prospect.

The present invention is according to applicant's industrialization pilot scale research and experience accumulation, and on probation through relevant producer, respond well.Leading indicators such as alumina content, density, basicity, pH value have reached the index request of HG/T2677-95 industry polymerize aluminum chloride, and along with continuous technical matters is improved, quality product progressively improves, and fact proved that our operational path is feasible.

Embodiment

Embodiment 1

5 tons coal gangue is joined reactor, and simultaneously implantation quality per-cent is 3 tons of 24% industrial waste salt acid, injects 2 tons in clear water, adding weight part is 0.2 ton Repone K, 0.22 ton calcium chloride, and in reactor, fully stir, reactor is airtight, prevent the acid volatilization.Injecting steam heats, and is heated to 100-110 ℃, reacts 2-3 hour.After reaction finishes material is cooled to 70-80 ℃ and carries out the separation of slag liquid.Parting liquid enters another reactor adding basicity adjustment agent and carries out the polymerization adjustment, and the time of controlled polymerization reaction is 1-2 hour, and temperature is 90-100 ℃.Polyreaction is finished postcooling to 70 and ℃ is carried out slag liquid while hot and separate, and parting liquid is a liquid product, and in its liquid product, the massfraction of aluminum oxide is 10.1%, and ferric oxide massfraction 1.4%, the massfraction of water-insoluble are 0.7%, and basicity is 58.Liquid product is solid phase prod through behind the concentrate drying.

Embodiment 2

5 tons slag is joined reactor, and simultaneously implantation quality per-cent is 3 tons of 24% industrial waste salt acid, injects 2 tons in clear water, and adding weight part is 0.2 ton sodium-chlor, and fully stirs in reactor, and reactor is airtight, prevents the acid volatilization.Injecting steam heats, and is heated to 110-120 ℃, reacts 2-3 hour.After reaction finishes material is cooled to 70-80 ℃ and carries out the separation of slag liquid.Parting liquid enters another reactor adding basicity adjustment agent and carries out the polymerization adjustment, and the time of controlled polymerization reaction is 1-2 hour, and temperature is 95-100 ℃.Polyreaction is finished postcooling to 70 and ℃ is carried out slag liquid while hot and separate, and parting liquid is a liquid product, and in its liquid product, the massfraction of aluminum oxide is 10.18%, and ferric oxide massfraction 1.5%, the massfraction of water-insoluble are 0.8%, and basicity is 81.Liquid product is solid phase prod through behind the concentrate drying.

Claims (1)

1, the method for utilizing plant slag, coal gangue to produce polyaluminum ferric chloride composite water purification agent, it comprises the steps:

Step 1 is pulverized: plant slag or colliery powder are broken to below the particle diameter 8mm;

Step 2 acid in small, broken bits is molten: the colliery powder after plant slag or the roasting is broken to about 60 orders, be that acid is molten continuously under 100～110 ℃ condition of normal pressure for 20% hydrochloric acid with mass concentration, the molten equipment of acid adopts the still method, use the steam direct heating, will stir in the molten process of acid, dissolution fluid carries out slag liquid with pressure filter to be separated;

Step 3 concentrates polymerization: the molten mother liquor of acid is sent in the enamel still, under negative pressure state, concentrate with steam heating, when the mother liquor concentration and evaporation falls 45～50%, stop heating and concentrate, drop into a certain amount of calcium aluminate powder then, carry out polyreaction and basicity adjustment reaction, after 2～4 hours reaction times, carry out naturally cooling, be cooled to about 60 ℃, carry out squeeze and filter once more, the liquid of extrusion is the polymerize aluminum chloride iron product.Or the molten mother liquor of acid is directly imported polymerization adjust the pond and heat, dropping into a certain proportion of calcium aluminate powder then and carry out polymerization and basicity adjustment, resultant is the aluminium iron polychloride finished product;

The adjustment of step 4 concentration: the aluminium iron polychloride with previous step is produced, carry out the water distribution adjustment according to the concentration that records proportion and requirement, produce liquid and can sell.

Step 5 as production solid phase prod, the liquid that step 3 can be generated is through cylinder dried or adopt the aerosol desiccating method to produce, and promptly obtains solid polyaluminium chloride iron finished product.