CN1325389C - Method for preparing poly aluminum silico-sulfate flocculant by using waste catalyst - Google Patents
Method for preparing poly aluminum silico-sulfate flocculant by using waste catalyst Download PDFInfo
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- CN1325389C CN1325389C CNB200410042786XA CN200410042786A CN1325389C CN 1325389 C CN1325389 C CN 1325389C CN B200410042786X A CNB200410042786X A CN B200410042786XA CN 200410042786 A CN200410042786 A CN 200410042786A CN 1325389 C CN1325389 C CN 1325389C
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- spent catalyst
- silicate
- aluminum sulfate
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- polymeric aluminum
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Abstract
The present invention relates to a method for preparing inorganic high molecular poly aluminum silico-sulfate flocculant by the catalysis of a waste catalyst by heavy oil. The present invention is characterized in that 3% of sulfuric acid directly dissolves heavy oil to catalyze a waste catalyst under the conditions that the liquid and solid ratio of the acid and the waste catalyst is 5 to 15: 1, reaction temperature is 80 to 100 DEG C, and reaction time is 1 to 2 hour; then, residue and 5% to 20% of sodium hydroxide prepare silicate under the conditions that the liquid and solid ratio of sodium hydroxide and the residue is 10: 1, the reaction temperature is 80 to 100 DEG C, and the reaction time is 1 to 2 hour; finally, aluminum salt and the silicate are polymerized to prepare liquid poly aluminum silico-sulfate. The present invention has the advantages that a feasible approach is supplied to the comprehensive utilization of industrial waste, and simultaneously, a technological line of cheap raw materials is supplied to the production of the flocculant. The flocculant is used for processing different waste water, the removal rate of COD<cr> achieves 37% to 67%, and turbidity removal rate achieves by more than 80%. A treatment effect is obvious, and thus, the treatment aim is achieved.
Description
Technical field
The present invention relates to a kind of method of utilizing the heavy-oil catalytic spent catalyst to prepare inorganic macromolecule compound one polymeric aluminum sulfate silicate flocculation agent.
Background technology
The general formula of polymeric aluminum sulfate silicate is Al (OH)
A(SO
4)
B(SiO
C) (H
2O)
D, the development of polymeric aluminum sulfate silicate salt starts from the latter stage eighties abroad, domesticly starts from the initial stage nineties.This flocculation agent has charge neutrality and adsorption bridging effect simultaneously, and flocculating effect is good.This flocculation agent has low price simultaneously, the remaining aluminium amount of handling in the water of back is low, can generate highdensity throw out, sedimentation is rapid, compares with other inorganic flocculating agent, renders a service constant under cold water temperature, to advantages such as equipment corrosion are little, therefore, cause the very big concern of field of water treatment, become a big focus of domestic and international inorganic flocculating agent research.
At present, the method for preparing polymeric aluminum sulfate silicate both at home and abroad mainly contains (1) and is prepared as raw material with ore, abandoned mine slag, flyash etc.; Effective concentration generally is lower than 10% in the products obtained therefrom, and the flocculating result of product is better than Tai-Ace S 150.(2) aluminium salt is incorporated in the poly-silicate solution and is prepared; Present domestic Harbin Institute of Technology has carried out the work of this respect, does not see relevant report abroad; (3) under the high shear process condition, be prepared as raw material with water glass, sodium aluminate and Tai-Ace S 150 etc.Handy company has built at Quebec, Canada Laprairie in 1991 and has produced 2.7 ten thousand tons factory per year, has built respectively and has produced 20000 tons factory per year in the U.S., Japan thereafter.China Shandong and Harbin all have company to produce the polymeric aluminum sulfate silicate flocculation agent.It is mainly used in sewage disposal and purifies waste water processing etc.Ecological from reducing production costs, reduce the three waste discharge protection
The angle of environment is set out, and it is very necessary selecting cost of material method cheap, that synthesis technique simply prepares polymeric aluminum sulfate silicate.
Refinery heavy-oil catalytic workshop produces spent catalyst in catalyst regeneration process, about 300 tons of the spent catalyst that refinery heavy-oil catalytic workshop year produces is stacked at outdoor contaminate environment, influences environment, and all there is the handling problem of spent catalyst in domestic each refinery.Prior art adopts substantially and adds the method for burying and handle handling on the spent catalyst of heavy-oil catalytic domestic each refinery, and the defective of this method is not only to cause the efficient resource waste, and its environmental hazard is serious.Utilize heavy-oil catalytic spent catalyst synthetic flocculant, can make spent catalyst utilized, all have profound significance from environment protection and the angle of creating economic benefit.
Domestic patent 90103195 (publication number: CN1049140A) introduced and adopt acid molten, adjust the method for base degree and handle this spent catalyst by gel aluminium hydroxide.This technology is that spent catalyst has been synthesized flocculant of polymeric aluminium chloride, and its defective is only to have solved the aluminum oxide part in the spent catalyst, does not handle for the silicon oxide of other parts.
Summary of the invention
The objective of the invention is to adopt heavy-oil catalytic workshop spent catalyst is raw material, and preparation polymeric aluminum sulfate silicate flocculation agent is developed an efficient ways and administered the heavy-oil catalytic spent catalyst, makes it can access appropriate processing, reduces environmental pollution.
Technical scheme of the present invention is: contain aluminium in the spent catalyst, the sulfuric acid of employing 3% is 5-15 in liquid-solid ratio (acid/spent catalyst): 1, temperature of reaction is 80-100 ℃, reaction times is 1-2 hour, directly sour molten heavy-oil catalytic spent catalyst obtains aluminium salt, using the sodium hydroxide of last slag and 5%-20% then is 10: 1 in liquid-solid ratio (alkali/spent catalyst), temperature of reaction is 80-100 ℃, reaction times is 1-2 hour, produce silicate, at last aluminium salt and silicate polymerization are made liquid polymeric aluminum sulfate silicate.
Best-of-breed technology scheme of the present invention is to adopt the sulfuric acid of concentration 3%, under 85 ℃ of temperature of reaction, 1 hour reaction times, 85 ℃ of dissolvings spent catalyst, wherein the liquid-solid proportioning of acid/spent catalyst is 10: 1 preparation aluminium salt, dissolves its filter residues with 10% sodium hydroxide down at 85 ℃ again and prepare silicate, be 3 with aluminium salt and silicate by equivalence ratio then, carry out polymerization, 1000 rev/mins of mixing speed, 0.5 hour reaction times is preparation polymeric aluminum sulfate silicate flocculation agent down.
Effect of the present invention: because refinery heavy-oil catalytic spent catalyst is formed complexity, difficulty of governance is big, and the spent catalyst that domestic same device produced does not all have corresponding treatment facility, so spent catalyst is all stacked outdoor or landfill.Acid of the present invention is molten, alkali is molten and polymerization process synthesizes the polymeric aluminum sulfate silicate flocculation agent, handles all kinds of waste water with this flocculation agent, and its CODcr clearance is in the 37%---67% scope, and turbidity removal rate has reached more than 80%.The present invention has not only solved the pollution problem of spent catalyst but also can utilize the spent catalyst synthetic flocculant, and the flocculating effect highly significant of this flocculation agent has reached the purpose that turns waste into wealth.As follows to economic analysis of the present invention:
1. cost (in the ton liquid product)
| The items of cost | Consumption | Unit price is former/ton | Total price unit/ton | Remarks |
| Spent catalyst acid 3%: alkali 10% electrician supports other total | 0.1 0.07 0.1 40 | 500 2500 0.5 | 35 250 20 100 30 300 |
Because main raw material is taken from spent catalyst, 300 yuan of left stones of liquid product production cost per ton.
2, selling price
Existing market price liquid product valency is at 1000---2000 unit/ton.
3, economic benefit
Price cost gross profit profit after tax
1000 300 700 550
Calculate with annual 300 tons of spent catalyst: can produce 3000 tons of liquid products;
Annual return: 3000*550=1650,000 yuan/year.
The present invention is that inorganic macromolecule compound is produced in comprehensive utilization industry " three wastes ", has favorable economic benefit.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Specific embodiments
The present invention is described in detail below in conjunction with accompanying drawing.
Embodiment 1
Utilizing spent catalyst to prepare the polymeric aluminum sulfate silicate liquid product may further comprise the steps:
(1) produce aluminium salt with spent catalyst and direct reaction of sulfuric acid: get concentration and be 3% sulfuric acid, soak molten spent catalyst, acid is 5: 1 with the liquid-solid weight proportion of spent catalyst, 100 ℃ of temperature of reaction, produces under the condition in 2 hours reaction times and obtains aluminium salt;
(2) with waste residue after the extraction aluminium salt and sodium hydroxide reaction, produce silicate: the sodium hydroxide with 20% dissolves its filter residue down at 80 ℃ and prepares silicate, and the liquid-solid weight proportion of sodium hydroxide and waste residue is 10: 1,1 hour reaction times.
(3) with aluminium salt and silicate, be 3 by equivalence ratio, carry out polymerization, 1000 rev/mins of mixing speed, prepare the polymeric aluminum sulfate silicate flocculation agent under 0.5 hour reaction times.
Chemical engineering sewage CODcr content 853mg/l, turbidity 500mg/l, with synthetic product and polymeric aluminum sulfate silicate finished product chemical engineering sewage is carried out flocculation treatment, the result who handles can handle 287mg/l from 853mg/l with the CODcr of chemical engineering sewage with spent catalyst synthetic polymeric aluminum sulfate silicate flocculation agent, turbidity is reduced to 100mg/l from 500mg/l, CODcr clearance 66.3%, turbidity removal rate 80%.The polymeric aluminum sulfate silicate flocculation agent of producer is handled 276mg/l with the CODcr of chemical engineering sewage from 853mg/l, and turbidity is reduced to 100mg/l from 500mg/l.CODcr clearance 67.6%.Turbidity removal rate 80%.This shows that the relative flocculating effect of institute's synthetic polymeric aluminum sulfate silicate is near commercial polymeric aluminum sulfate silicate.
Embodiment 2
Utilizing spent catalyst to prepare the polymeric aluminum sulfate silicate liquid product may further comprise the steps:
(1) produce aluminium salt with spent catalyst and direct reaction of sulfuric acid: get concentration and be 3% sulfuric acid, soak molten spent catalyst, acid is 10: 1 with the liquid-solid weight proportion of spent catalyst, 85 ℃ of temperature of reaction, produces under the condition in 1 hour reaction times and obtains aluminium salt;
(2) with waste residue after the extraction aluminium salt and sodium hydroxide reaction, produce silicate: the sodium hydroxide with 10% dissolves its filter residue down at 85 ℃ and prepares silicate, and the liquid-solid weight proportion of sodium hydroxide and waste residue is 10: 1,1 hour reaction times.
(3) with aluminium salt and silicate, be 3 by equivalence ratio, carry out polymerization, 1000 rev/mins of mixing speed, prepare the polymeric aluminum sulfate silicate flocculation agent under 0.5 hour reaction times.
ABS COD of sewage cr content 529mg/l, turbidity 2000mg/l, with synthetic product and polymeric aluminum sulfate silicate finished product ABS sewage is carried out flocculation treatment, the result who handles can handle 166mg/l from 629mg/l with the CODcr of ABS sewage with spent catalyst synthetic polymeric aluminum sulfate silicate flocculation agent, turbidity is reduced to 100mg/l from 2000mg/l, CODcr clearance 68.6%, turbidity removal rate 95%.The polymeric aluminum sulfate silicate flocculation agent of producer is handled 157mg/l with the CODcr of ABS sewage from 529mg/l, and turbidity is reduced to 100mg/l from 2000mg/l, CODcr clearance 70.03%, turbidity removal rate 95%.This shows that the relative flocculating effect of institute's synthetic polymeric aluminum sulfate silicate is near commercial polymeric aluminum sulfate silicate.
Embodiment 3:
Utilizing spent catalyst to prepare the polymeric aluminum sulfate silicate liquid product may further comprise the steps:
(1) produce aluminium salt with spent catalyst and direct reaction of sulfuric acid: get concentration and be 3% sulfuric acid, soak molten spent catalyst, acid is 15: 1 with the liquid-solid weight proportion of spent catalyst, 80 ℃ of temperature of reaction, produces under the condition in 2 hours reaction times and obtains aluminium salt;
(2) with waste residue after the extraction aluminium salt and sodium hydroxide reaction, produce silicate: the sodium hydroxide with 5% dissolves its filter residue down at 100 ℃ and prepares silicate, and the liquid-solid weight proportion of sodium hydroxide and waste residue is 10: 1,1 hour reaction times.
(3) with aluminium salt and silicate, be 3 by equivalence ratio, carry out polymerization, 1000 rev/mins of mixing speed, prepare the polymeric aluminum sulfate silicate flocculation agent under 0.5 hour reaction times.
Acrylon sewage CODcr content 341mg/l, turbidity 800mg/l, with synthetic product and polymeric aluminum sulfate silicate finished product acrylon sewage is carried out flocculation treatment, the result who handles can handle 211mg/l from 348mg/l with the CODcr of acrylon sewage with spent catalyst synthetic polymeric aluminum sulfate silicate flocculation agent, turbidity is reduced to 100mg/l from 800mg/l, CODcr clearance 39.4%, turbidity removal rate 87.5%.The polymeric aluminum sulfate silicate flocculation agent of producer is handled 220 mg/l with the CODcr of acrylon sewage from 348mg/l, and turbidity is reduced to 100mg/l from 800 mg/l, CODcr clearance 36.8%, turbidity removal rate 87.5%.This shows that the relative flocculating effect of institute's synthetic polymeric aluminum sulfate silicate is near commercial polymeric aluminum sulfate silicate.
Claims (4)
1. method for preparing the polymeric aluminum sulfate silicate flocculation agent with spent catalyst, it is characterized in that: contain aluminium in the spent catalyst, sulfuric acid with 3% is 5-15 in acid with spent catalyst weight liquid-solid ratio: 1, temperature of reaction is 80-100 ℃, reaction times is 1-2 hour, directly sour molten heavy-oil catalytic spent catalyst obtains aluminium salt, sodium hydroxide with last slag and 5%-20% is 10: 1 at alkali and slag weight liquid-solid ratio then, temperature of reaction is 80-100 ℃, reaction times is 1-2 hour, produce silicate, at last aluminium salt and silicate polymerization are made liquid polymeric aluminum sulfate silicate.
2. according to claim 1ly prepare the method for polymeric aluminum sulfate silicate flocculation agent, it is characterized in that with spent catalyst: direct sour molten heavy-oil catalytic spent catalyst, acid is 10: 1 with spent catalyst weight liquid-solid ratio, and temperature of reaction is 85 ℃, and the reaction times is 1 hour.
3. according to claim 1ly prepare the method for polymeric aluminum sulfate silicate flocculation agent with spent catalyst, it is characterized in that: with the molten last slag of 10% sodium hydroxide alkali, temperature of reaction is 85 ℃, and the reaction times is 1 hour.
4. according to claim 1ly prepare the method for polymeric aluminum sulfate silicate flocculation agent with spent catalyst, it is characterized in that: stirring velocity is polymerization under 1000 rev/mins of conditions when polyaluminium salts and silicate, 0.5 hour reaction times.
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|---|---|---|---|
| CNB200410042786XA CN1325389C (en) | 2004-05-28 | 2004-05-28 | Method for preparing poly aluminum silico-sulfate flocculant by using waste catalyst |
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| CNB200410042786XA CN1325389C (en) | 2004-05-28 | 2004-05-28 | Method for preparing poly aluminum silico-sulfate flocculant by using waste catalyst |
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| CN1704350A CN1704350A (en) | 2005-12-07 |
| CN1325389C true CN1325389C (en) | 2007-07-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304012B (en) * | 2012-03-08 | 2014-12-31 | 中国石油化工股份有限公司 | Method of preparing flocculant by using sewage residues of refinery catalyst plant |
| CN110627099B (en) * | 2019-11-06 | 2021-09-17 | 山东聚杰环保科技有限公司 | Method for preparing high-purity aluminum sulfate and co-producing poly-silicon ferric aluminum sulfate by using waste catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059505A (en) * | 1991-09-28 | 1992-03-18 | 张伯温 | Polymeric silicicacid-aluminium composite flocculation agent and preparation method |
| CN1299783A (en) * | 2000-12-22 | 2001-06-20 | 华南理工大学 | Polymerized basic aluminosilicate flocculant and its preparation process and equipoment |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059505A (en) * | 1991-09-28 | 1992-03-18 | 张伯温 | Polymeric silicicacid-aluminium composite flocculation agent and preparation method |
| CN1299783A (en) * | 2000-12-22 | 2001-06-20 | 华南理工大学 | Polymerized basic aluminosilicate flocculant and its preparation process and equipoment |
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