CN103030200A

CN103030200A - Method for producing poly-silicon rare earth chloride sulfate aluminum iron by using rare earth-containing sludge and electroplated and pickled acid-containing sewage

Info

Publication number: CN103030200A
Application number: CN2013100066894A
Authority: CN
Inventors: 杨祺
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-01-09
Filing date: 2013-01-09
Publication date: 2013-04-10

Abstract

The invention belongs to the technical field of preparation of a polymeric flocculant for sewage treatment and particularly relates to a method for producing poly-silicon rare earth chloride sulfate aluminum iron by using rare earth-containing sludge and electroplated and pickled acid-containing sewage. The method comprises the following steps: raw material mixing and acidolysis as well as three steps of oxidization, hydrolysis and polymerization. The method has the beneficial effects that a new production process for preparing the polymeric flocculant by using the rare earth-containing sewage sludge produced by a petrochemical catalyst production enterprise and the pickled acid-containing sewage produced by an electroplating enterprise as main raw materials is provided; the process of producing the poly-silicon rare earth chloride sulfate aluminum iron is simplified, the production time is shortened, the product stability is good, and the performance is excellent; and meanwhile, a new way is provided for the utilization of the rare earth-containing sludge and the electroplated and pickled acid-containing sewage, the comprehensive resource utilization rate is improved, and the production cost and the sewage treatment cost of the poly-silicon rare earth chloride sulfate aluminum iron flocculant are also reduced, therefore, the economic benefit, the environmental protection benefit and the social benefit are high.

Description

With containing rare earth mud and electroplating the method that pickling contains the poly-silicon sulfuric acid rare earth chloride ferro-aluminum of sour sewage production

One, technical field:

The invention belongs to sewage disposal polymeric flocculant preparing technical field, be specifically related to containing rare earth mud and electroplating the method that pickling contains the poly-silicon sulfuric acid rare earth chloride ferro-aluminum of sour sewage production.

Two, background technology:

The existing raw material of producing polymeric aluminum sulfate silicate iron has water glass, ferric sulfate, Tai-Ace S 150, aluminum chloride, Tai-Ace S 150, and production method is with behind the poly-silicic acid of water glass acidifying preparation, introduces iron again, aluminum ion is polymerized.This production method needs expensive industrial chemicals, and cost is higher.And ZL200510094967.1 " method for preparing poly-silicon iron aluminium sulphate with metallurgical slag ", although found a kind of approach of producing polymeric aluminum sulfate silicate iron production cost that reduces, effective concentration content is lower, poor stability.

Three, summary of the invention:

The objective of the invention is in view of the foregoing defects the prior art has, plan provides a kind of usefulness that is different from the prior art scheme to contain rare earth mud and electroplates the method that pickling contains the poly-silicon sulfuric acid rare earth chloride ferro-aluminum of sour sewage production, make it technological process and condition is simple, the investment of production equipment expense is less, process cost is low, product performance are stable, and are superior in quality.

For realizing purpose of the present invention, the technical scheme of taking is as follows:

With containing rare earth mud and electroplating the method that pickling contains the poly-silicon sulfuric acid rare earth chloride ferro-aluminum of sour sewage production, it is characterized in that it is main raw material that pickling that it comprises that the sewage sludge that contains rare earth that produces with Effect of Catalysis In Petrochemistry agent manufacturing enterprise and electroplating enterprise produce contains sour sewage, is that it is comprised of three step processes:

1. produce main raw material and the chemical composition of poly-silicon sulfuric acid rare earth chloride ferro-aluminum:

The main raw material that the present invention relates to is that the sewage sludge of Effect of Catalysis In Petrochemistry agent manufacturing enterprise generation and the pickling of electroplating enterprise generation contain sour sewage.The sewage sludge that Effect of Catalysis In Petrochemistry agent manufacturing enterprise produces is that Effect of Catalysis In Petrochemistry agent manufacturing enterprise is in producing the catalyst prod process, the PH that produces＜4 sewage neutralize with NaOH, make sewage PH＞9 carry out sewage disposal with sewage treatment process again, the mud that in sewage treatment process, produces, its chemical composition sees Table 1, and the SiO2 that contains in this mud, AL2O3, La2O3, CeO2 component are the raw material sources that the method is produced poly-silicon sulfuric acid rare earth chloride ferro-aluminum.Contain sour sewage, source and the acid cleaning process of electroplating industry, its chemical composition sees Table 2, table 3, and the H2SO4 that contains in this sewage, HCL, FeCL3, FeCL2, AL2 (SO4) 3 components are raw material sources that the method is produced poly-silicon sulfuric acid rare earth chloride ferro-aluminum.

Table 1. is produced the main chemical compositions of the sewage sludge of Effect of Catalysis In Petrochemistry agent enterprise

Table 2. is electroplated the main chemical compositions that pickling contains sour sewage

Electroplating pickling contains sour sewage two kinds in sulfur acid sewage and hydrochloric sewage is arranged; Sulfur acid sewage is less; Hydrochloric sewage is more, and existing treatment process major part all is to enter Waste Water Treatment to process with the acid-base neutralisation chemical mode, and cost is high, the mud amount is large, and that the mud of generation is processed is difficult, easily produce secondary pollution.

Sulfur acid sewage output wherein contains AL2 (SO4) 3, sulfuric acid about 15% at most at the oxidation section of anod surface treatment factory.

Hydrochloric sewage output in workshop section of iron material pickling factory (cold rolled pickling steel sheets, the pickling of fastening piece iron wire), wherein contains FeCL3, FeCL2, hydrochloric acid about 10% at most.

Table 2. is electroplated the main chemical compositions of pickling sulfur acid sewage

Table 3. is electroplated the main chemical compositions of the hydrochloric sewage of pickling

2. production process:

(1)。To contain rare earth mud, sulfur acid sewage, hydrochloric sewage by weight percentage (0.1-0.3): 1: 1 abundant mixing was put into acid-resistant reacting kettle, carry out acidolysis to containing rare earth mud, fully stirred 1 hour, the question response system is cooled to room temperature, and acidolysis reaction finishes.

(2)。Reaction product is filtered removal throw out (being mainly acid non-soluble substance), the H2O2 of filtrate (being mainly the mixing solutions of ferrous salt, trivalent iron salt, aluminium salt, lanthanum salt, cerium salt and silicate hydrate) with 27.5% makes that Fe2+ all is oxidized to Fe3+ in the solution, and its oxidation terminal point of the process of Oxidation of Fe 2+ is determined with the Tripotassium iron hexacyanide; Adjusting the solution pH value with 30%NaOH again is 2.0-2.5; Solution after adjusting is placed heating in water bath 1-2 hour, maintain the temperature at about 80 ℃, make that solution after the adjustment is hydrolyzed voluntarily, polymerization, the liquid product of reddish brown occurs, be the poly-ferric aluminum silicate sulfate from rare earth flocculation agent.

The present invention gel do not occur by the previous process steps products obtained therefrom in 2 months, product performance are more stable.

Compared with prior art the present invention has following unusual effect:

1, the sewage sludge of Effect of Catalysis In Petrochemistry agent manufacturing enterprise generation is that Effect of Catalysis In Petrochemistry agent manufacturing enterprise is in producing the catalyst prod process, the PH that produces＜4 sewage neutralize with NaOH, make sewage PH＞9 carry out sewage disposal with sewage treatment process again, the mud that in sewage treatment process, produces, make the SiO2 in the mud be converted into Na2SiO3, for acidifying, hydrolysis, polyreaction have been created condition.

2, the sewage sludge of Effect of Catalysis In Petrochemistry agent manufacturing enterprise generation is the mud that produces in the sewage treatment process of Effect of Catalysis In Petrochemistry agent manufacturing enterprise in producing the catalyst prod process, the La2O3 that contains in this mud, CeO2s component play oxidation, katalysis in producing poly-silicon sulfuric acid rare earth chloride ferro-aluminum technique, shortened Fe2+ and be converted into time of Fe3+ and the acidolysis of poly-silicon sulfuric acid aluminum ferric chloride, hydrolysis, polymerization time.In addition, poly-silicon sulfuric acid rare earth chloride ferro-aluminum is because La2O3, CeO2 participate in the chemical reaction of poly-silicon sulfuric acid aluminum ferric chloride polymerization, changed the molecular structure of poly-silicon sulfuric acid aluminum ferric chloride flocculating agent, formed than poly-silicon sulfuric acid aluminum ferric chloride complex molecule volume large poly-silicon sulfuric acid rare earth chloride ferro-aluminum complex molecule also, the wastewater treatment efficiency of this complex molecule will be considerably beyond the wastewater treatment efficiency of existing polymeric aluminum sulfate silicate iron, poly-silicon aluminium chloride ferrum complex molecule.

In a word, usefulness of the present invention contains rare earth mud and electroplates the method that pickling contains the poly-rare upper ferro-aluminum of silicon sulfuric acid chlorination of sour sewage production, and the poly-silicon sulfuric acid rare earth chloride ferro-aluminum flocculation agent of producing is suitable for processing high-concentration sewage, sanitary sewage, industrial sewage.This production method has been simplified technological process, has shortened the production time, and product stability is good, excellent property; Provide new approach for containing rare earth mud and electroplating the utilization that contains sour sewage simultaneously, improved the comprehensive utilization of resources rate, also reduce production cost and the cost of sewage disposal of poly-silicon sulfuric acid rare earth chloride ferro-aluminum flocculation agent, had very high economic benefit, environmental benefit and social benefit.

Four, embodiment:

Example one:

(1)。To contain rare earth mud, sulfur acid sewage, 0.1: 1: 1 by weight percentage abundant mixing of hydrochloric sewage put into acid-resistant reacting kettle, and carry out acidolysis to containing rare earth mud, fully stir 1 hour, the question response system is cooled to room temperature, and acidolysis reaction finishes.

Example two:

(1)。To contain rare earth mud, sulfur acid sewage, 0.3: 1: 1 by weight percentage abundant mixing of hydrochloric sewage put into acid-resistant reacting kettle, and carry out acidolysis to containing rare earth mud, fully stir 1 hour, the question response system is cooled to room temperature, and acidolysis reaction finishes.

Claims

1. one kind with containing rare earth mud and electroplating the method that pickling contains the poly-silicon sulfuric acid rare earth chloride ferro-aluminum of sour sewage production, it is characterized in that it comprises that with the sewage sludge that contains rare earth of Effect of Catalysis In Petrochemistry agent manufacturing enterprise generation and sulfur acid, the hydrochloric sewage of Electroplating Production enterprise generation be raw material, is that it is comprised of two step processes:

(1)。To contain rare earth mud, sulfur acid sewage, hydrochloric sewage by weight percentage (0.1-0.3): 1: 1 abundant mixing was put into acid tolerance response Fu, carry out acidolysis to containing rare earth mud, fully stirred 1 hour, the question response system is cooled to room temperature, and acidolysis reaction finishes.

(2)。Reaction product is filtered removal throw out (being mainly acid non-soluble substance), the H2O2 of filtrate (being mainly the mixing solutions of ferrous salt, trivalent iron salt, aluminium salt, lanthanum salt, cerium salt and silicate hydrate) with 27.5% makes that Fe2+ all is oxidized to Fe3+ in the solution, and its oxidation terminal point of the process of Oxidation of Fe 2+ is determined with the Tripotassium iron hexacyanide; Adjusting the solution pH value with 30%NaOH again is 2.0-2.5; Solution after adjusting is placed heating in water bath 1-2 hour, maintain the temperature at about 80 ℃, make that solution after the adjustment is hydrolyzed voluntarily, polymerization, the liquid product of reddish brown occurs, be poly-silicon sulfuric acid rare earth chloride ferro-aluminum flocculation agent.