CN104030649A - Production process for high-strength high-volume phosphogypsum baking-free brick - Google Patents

Production process for high-strength high-volume phosphogypsum baking-free brick Download PDF

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CN104030649A
CN104030649A CN201410252707.1A CN201410252707A CN104030649A CN 104030649 A CN104030649 A CN 104030649A CN 201410252707 A CN201410252707 A CN 201410252707A CN 104030649 A CN104030649 A CN 104030649A
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phosphogypsum
strength
admixtion
baking
adobe
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CN104030649B (en
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周俊
于冬雪
舒杼
王焰新
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China University of Geosciences
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Abstract

The invention relates to a production process for a high-strength high-volume phosphogypsum baking-free brick. The production process comprises the following steps: (1), material pre-treating: mixing phosphogypsum with quick lime to obtain a material mixture, placing the material mixture in drying machinery for drying at 180 DEG C under a normal pressure condition after aging for one day to obtain a dehydrated phosphogypsum-quick lime neutralized material; (2), preparing materials: weighing the dehydrated phosphogypsum-quick lime neutralized material and yellow sand according to a proportion, adding into a stirrer for stirring and uniformly mixing to obtain mixed batch which comprises the following components in percent by weight: 70%-90% of dehydrated phosphogypsum-quick lime neutralized material, and 10%-30% of yellow sand; (3), watering and stirring; (4), pressing and forming; (5), soaking in water and hydrating; and (6), drying. The method provided by the invention is simple in step, not mixed with cement, and low in cost; and moreover, the prepared phosphogypsum baking-free brick is high in strength and suitable for industrial production.

Description

The production technique of the high content phosphor-gypsum baking-free bricks of high strength
Technical field
The invention belongs to building material technical field, be specifically related to the production technique of the high content phosphor-gypsum baking-free bricks of a kind of high strength.
Background technology
Phosphogypsum is the industrial solid wastes that discharge in Wet-process Phosphoric Acid Production process.In Wet-process Phosphoric Acid Production process, common every production 1t phosphoric acid is (with 100% P 2o 5calculate) approximately produce the phosphogypsum of 4.5~5.5t.Phosphogypsum main component is terra alba (CaSO 42H 2o), contain in addition a small amount of other impurity, be slightly acidic, viscosity is stronger.In phosphogypsum, the impurity such as contained fluorochemical, free phosphoric acid, phosphoric acid salt is the principal element that causes environmental pollution.
Phosphogypsum, for the production of construction wall brick, is the phosphogypsum of can dissolving in a large number, realizes the effective way of phosphogypsum resource utilization.At present, the production technique of phosphogypsum manufacture construction wall brick can be divided into two classes, i.e. ardealite baked brick production technique and baking-free ardealite brick production technique substantially.
Ardealite baked brick production technique is generally: 1. raw materials pretreatment, 2. batching, 3. mix and blend, 4. compacting (or extruding) moulding, 5. seasoning, 6. high-temperature roasting, 7. annealing cooling, 8. finished product.If China Patent Publication No. is as shown in the patents such as CN1381423A, CN1465540A, CN101774797A, CN102503517A, CN103044007A.The main deficiency of this technique is: (1) energy consumption is high: this technique need to continuous roasting be not less than 30h, the heat energy that this process need consumption is a large amount of conventionally under 700~900 DEG C of high temperature; (2) there is secondary pollution: decomposition reaction can occur the main component terra alba of phosphogypsum in high-temperature calcination process, discharges oxysulfide, can cause secondary pollution to atmosphere.
Baking-free ardealite brick production technique can effectively overcome the deficiency in above-mentioned ardealite baked brick production.Active service baking-free ardealite brick production technique mainly contains two classes: a class is compression moulding vapor cure brickmaking production technique (being designated hereinafter simply as " steamed brick technique "); Another kind of is the non-evaporating foster brickmaking production technique of high pressure compression moulding (being designated hereinafter simply as " high-pressure molding brickwork skill ").
Steamed brick technique is generally: 1. raw materials pretreatment, 2. batching, 3. mix and blend, 4. compacting (or extruding) moulding, 5. steam press maintenance (or hydrothermal curing), 6. seasoning, 7. finished product.If China Patent Publication No. is as shown in the patents such as CN101269944A, CN101497516A, CN101684675A, CN101637936A, CN1915894A, CN1955141A, CN101830677A, CN101891438A, CN103626461A, CN102701619A, CN102775118A.The main deficiency that this technique exists has: (1) energy consumption is higher.This technique needs steam press maintenance (or hydrothermal curing), and while adopting low temperature (80 DEG C~100 DEG C), steam press maintenance needs the time longer, generally needs 8h~24h; If while adopting high temperature (120 DEG C~250 DEG C), steam press maintenance needs the time relatively short, but still needs 5h~10h; (2) production unit requires high.Steam press maintenance needs special maintenance of equipment, is often steam-cured (pressure) still, and this equipment need to have higher stopping property, higher to equipment and materials and structural requirement, and maintenance cost is also larger.In view of the foregoing, the production cost of this explained hereafter baking-free ardealite brick is higher.
High-pressure molding brickwork skill is generally: 1. raw materials pretreatment, 2. batching, 3. mix and blend, 4. high pressure compression moulding, 5. seasoning, 6. finished product.If China Patent Publication No. is as shown in the patents such as CN1277168A, CN1673154A, CN101508556A, CN101182179A, CN101397205A, CN202338056U, CN1935736A.The main deficiency that this technique exists is at present: (1) product strength is low.Non-burning brick ultimate compression strength prepared by this technique is usually less than 10MPa, and the use range of product is very restricted; (2) forming pressure is large, and equipment requirements is high, and forming pressure is generally greater than 40MPa, and even up to 80MPa, therefore compression molding device material and structural requirement are all higher, power consumption consumption is also larger.
In addition, in producing, baking-free ardealite brick generally also wants admixture cement or other tackiness agent.As the China Patent Publication No. cement that has been the admixtures such as CN101475359, CN101508556A; The China Patent Publication No. tackiness agent that has been the admixtures such as CN102276228A, CN1277168A.A large amount of admixtures of cement or tackiness agent cause non-burning brick production cost high, are unfavorable for large-scale promotion application.
In order to improve the physical strength of product, China Patent Publication No. CN103641426A is based on above-mentioned " steamed brick technique ", by admixture yellow phosphorus furnace slag, unslaked lime as tackiness agent, make non-burning brick higher than 30MPa of ultimate compression strength, but the phosphogypsum optimum adding quantity of pulverized in this patent is only 30%, should regard auxiliary material as, and yellow phosphorus furnace slag volume is up to 50%, main raw material, therefore this non-burning brick product belongs to the non-burning brick of Yellow phosphorus furnace slag in essence.The Chinese invention patent CN102172968B that the inventor applies for, design an aquation recrystallizing technology, can prepare the baking-free ardealite brick of ultimate compression strength higher than 20MPa, but still there is the obstacle in some application in this technique, if needs admixture cement (3~10%) is as auxiliary
Help jelling agent, the required pressure of compression moulding (15~30MPa) bigger than normal.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, and a kind of technique of preparing baking-free ardealite brick taking phosphogypsum as main raw material is provided, and cost is low, technique is simple, and prepared baking-free ardealite brick intensity is high, and applied range, is suitable for scale operation.
The present invention is for solving the problems of the technologies described above by the following technical solutions:
A production technique for the high content phosphor-gypsum baking-free bricks of high strength, it comprises the following steps:
(1) raw materials pretreatment: phosphogypsum is mixed with unslaked lime, obtain compound, after old 1 day, compound is placed under drying machinery condition of normal pressure in 180 DEG C of dry dehydrated phosphogypsum-neutralization with lime material that obtain;
(2) batching: take in proportion dehydrated phosphogypsum-neutralization with lime material and yellow sand, drop in agitator and be uniformly mixed, make admixtion, in admixtion, the quality proportioning of each component is: dehydrated phosphogypsum-neutralization with lime material of 70~90%, 10~30% yellow sand;
(3) water mixing is stirred: in admixtion, add water, the mass ratio of admixtion and water is 100:18~25, is fully uniformly mixed and obtains water mixing admixtion;
(4) compression moulding: water mixing admixtion is inserted in brick pressing machine, and compression moulding under 8~12MPa pressure, obtains raw adobe;
(5) soaked aquation: under room temperature, life adobe is placed in to water and soaks 0.5~2h, obtain aquation adobe;
(6) dry: by aquation adobe dry 7 days under field conditions (factors), to make the high content phosphor-gypsum baking-free bricks of high strength.
The present invention, using the phosphogypsum that is converted into semi-hydrated gypsum through pre-treatment as raw material, mixes with fine aggregate yellow sand; A certain amount of water of admixture again, and the in time compression moulding adobe of making a living, now, water and semi-hydrated gypsum generation hydration reaction in raw adobe, make part unordered, semi-hydrated gypsum compacts separate, short texture is converted into that pattern is regular, mutual dihydrate gypsum gel interlock, compact structure; Finally by soaked hydration process, make remaining semi-hydrated gypsum continue to occur water reaction, final be all converted into pattern regular, dihydrate gypsum gel interlock, compact structure mutually, thereby give adobe up to ultimate compression strength more than 25MPa, make high strength baking-free ardealite brick product.
In experimentation, find: if the excessive water of admixture in step (3) water mixing stirring, on the one hand, there will be sticking to mould, bleeding etc. to be unfavorable for the phenomenon of step (4) compression moulding operation, on the other hand, semi-hydrated gypsum in raw adobe complete aquation in step (3) water mixing whipping process is converted into dihydrate gypsum, but in this process, material is not also by complete densification, the dihydrate gypsum that hydration reaction is produced can not be interlocked well mutually, finally causes the physical strength of non-burning brick product on the low side.If without the soaked aquation operation of step (5), part semi-hydrated gypsum in raw adobe after compression moulding is not by complete aquation so, also the dihydrate gypsum that generates mutual interlock by semi-hydrated gypsum hydration reaction increases considerably the effect of product physical strength and just can not give full play of, and result still causes the physical strength of non-burning brick product on the low side.In sum, only have by effective combination of step of the present invention (3) water mixing stirring and the soaked aquation of step (5), just can make semi-hydrated gypsum fully hydration reaction be converted into the dihydrate gypsum of mutual interlock, increase substantially the physical strength of adobe, obtain high-intensity baking-free ardealite brick.
The phosphogypsum of indication of the present invention is the industrial solid wastes that discharge in Wet-process Phosphoric Acid Production process, and the byproduct phosphogypsum that sulfuric acid decomposing phosphate rock stone produces uses other industrial gypsums, desulfurated plaster etc. but do not get rid of; Described yellow sand is common building river sand, water ratio≤5%, and sand rain size≤2.36mm, also can be rock crushing sand; Described unslaked lime is common building unslaked lime, and performance meets JC/T621-2009 " silicate building products unslaked lime " technical requirements; Described non-burning brick product both can be produced into solid brick, was also produced into hollow brick.
Production technique ultimate principle of the present invention is:
A, by step (1) raw materials pretreatment, (be terra alba CaSO by the dihydrate gypsum in phosphogypsum 42H 2o) being converted into semi-hydrated gypsum (is calcium sulphate hemihydrate CaSO 40.5H 2o);
B, by step (3) water mixing stir, to a certain amount of water of admixture in admixtion, and in time by step (4) compression moulding, water mixing admixtion is pressed into fine and close raw adobe, now, water and part semi-hydrated gypsum generation hydration reaction in raw adobe, generate dihydrate gypsum crystal, gives raw adobe certain physical strength;
C, due to step (3) water mixing stir in watering quantity be not enough to and all semi-hydrated gypsum generation hydration reactions, there is not hydration reaction in inevitable some semi-hydrated gypsum, therefore, by the soaked aquation of step (5), can make remaining semi-hydrated gypsum and water that sufficient hydration reaction occurs, all generate the dihydrate gypsum crystal of mutual interlock, give the physical strength that adobe is larger, again after step (6) is dry, finally can make more than 7 days ultimate compression strength of adobe reach 25MPa, thereby obtain high-intensity baking-free ardealite brick product.
Press such scheme, step (1) described time of drying is 1h.
Press such scheme, the described phosphogypsum of step (1) is 100:2 with Lime Quality ratio.
Press such scheme, described yellow sand water ratio≤5% of step (2), sand rain size≤2.36mm.
Beneficial effect of the present invention is:
1, the intensity of non-burning brick product is high.Through the semi-hydrated gypsum (CaSO in pretreated phosphogypsum 40.5H 2o) be after two step hydration reactions, to be just converted into dihydrate gypsum (CaSO completely 42H 2o), that is, the first step, strictly controls the watering quantity of step (3) water mixing in stirring, only make water in raw adobe can with part semi-hydrated gypsum generation hydration reaction, generate dihydrate gypsum crystal, give raw adobe certain physical strength; Second step, by the soaked aquation of step (5), make remaining semi-hydrated gypsum and water that sufficient hydration reaction occur, the dihydrate gypsum crystal of the mutual interlock of full scale production, give the very high physical strength of adobe (ultimate compression strength was greater than 25MPa in 7 days), meet the standard-required of the normal intensity grade MU25 of JC/T422-2007 " non-sintering rubbish tailing-bricks ";
2, phosphogypsum volume is high.The present invention is by the control of processing step, make semi-hydrated gypsum at twice aquation recrystallization be dihydrate gypsum gel, there is this qualitative difference with the steam-cured original position recrystallizing technology of existing high-temperature pressurizing principle, cause the volume of phosphogypsum in formula can be up to more than 80.0%, therefore, phosphogypsum is produced when non-burning brick and can be dissolved in a large number in the present invention, be conducive to increase substantially the recycling efficiency of phosphogypsum, store up the environmental problem that placement produces an effective approaches and methods is provided for solving phosphogypsum;
3, do not need admixture cement or tackiness agent.As mentioned above, by processing step of the present invention, can give full play to the gelling characteristic of phosphogypsum, can produce without admixture cement or tackiness agent the baking-free ardealite brick that intensity is high, this is conducive to significantly reduce raw materials cost;
4, production energy consumption is low.In existing steamed brick technique, adopt high-temperature pressurizing condition to carry out long-time steam press maintenance to adobe, energy consumption is higher; And in the present invention, it is only drying treatment 1h under the condition of 180 DEG C in normal pressure, temperature that drying and dehydrating is processed, energy consumption can significantly reduce, and requires low to drying plant;
5, production technique is simple, workable.Compared with the prior art, without steam-cured still, compression moulding only needs the pressure of 8~12MPa, and conventional brick pressing machine can meet need of production, without high pressure brick pressing machine; Soaked aquation operation is directly the raw adobe after compression moulding to be immersed in to 0.5~2h in room temperature water, and operation is simple.Whole processing step requires low, gentle to manufacturing condition requirement to production unit, be easy to production operation.
Brief description of the drawings
Fig. 1 is the process flow sheet that the embodiment of the present invention 1 is prepared the high content phosphor-gypsum baking-free bricks of high strength.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
As shown in Figure 1, the production technique of the present embodiment comprises the following steps process flow sheet:
(1) raw materials pretreatment: first by phosphogypsum with unslaked lime in mass ratio for 100:2 mixes, old 1 day so that the residual acid in phosphogypsum is fully neutralized by unslaked lime; Again this compound is placed in to drying machinery and under 180 DEG C and condition of normal pressure, carries out drying and dehydrating and process 1h, obtain dehydrated phosphogypsum-neutralization with lime material;
(2) batching: take dehydrated phosphogypsum-neutralization with lime material, yellow sand, 2 kinds of shared mass percents of raw material are: 80% dehydrated phosphogypsum-neutralization with lime material, 20% yellow sand, drop in agitator and be uniformly mixed, make admixtion;
(3) water mixing is stirred: to admixture water in admixtion, the mass ratio of admixtion and watering quantity is 100:22, is uniformly mixed fully, obtains water mixing admixtion;
(4) compression moulding: by water mixing admixtion cloth in brick pressing machine, the compression moulding adobe of making a living under 10MPa pressure;
(5) soaked aquation: life adobe is placed in to room temperature water and soaks 1h, make aquation adobe;
(6) seasoning: by aquation adobe dry 7 days under field conditions (factors), make baking-free ardealite brick product.
(taking compression moulding time start to calculate) intensity test value was 30.4MPa 7 days of the prepared baking-free ardealite brick product of the present embodiment, met the standard-required of the 25MPa ultimate compression strength of JC/T422-2007 " non-sintering rubbish tailing-bricks " (grade MU25).
Embodiment 2
The production technique of the present embodiment comprises the following steps:
(1) raw materials pretreatment: first by phosphogypsum with unslaked lime in mass ratio for 100:2 mixes, old 1 day so that the residual acid in phosphogypsum is fully neutralized by unslaked lime; Again this compound is placed in to drying machinery and under 180 DEG C and condition of normal pressure, carries out drying and dehydrating and process 1h, obtain dehydrated phosphogypsum-neutralization with lime material;
(2) batching: take dehydrated phosphogypsum-neutralization with lime material, yellow sand, 2 kinds of shared mass percents of raw material are: 90% dehydrated phosphogypsum-neutralization with lime material, 10% yellow sand, drop in agitator and be uniformly mixed, make admixtion;
(3) water mixing is stirred: to admixture water in admixtion, the mass ratio of admixtion and watering quantity is 100:25, is uniformly mixed fully, obtains water mixing admixtion;
(4) compression moulding: by water mixing admixtion cloth in brick pressing machine, the compression moulding adobe of making a living under 12MPa pressure;
(5) soaked aquation: life adobe is placed in to room temperature water and soaks 2h, make aquation adobe;
(6) seasoning: by aquation adobe dry 7 days under field conditions (factors), make baking-free ardealite brick product.
(taking compression moulding time start to calculate) intensity test value was 28.7MPa 7 days of the prepared baking-free ardealite brick product of the present embodiment, met the standard-required of the 25MPa ultimate compression strength of JC/T422-2007 " non-sintering rubbish tailing-bricks " (grade MU25).
Embodiment 3
The production technique of the present embodiment comprises the following steps:
(1) raw materials pretreatment: first by phosphogypsum with unslaked lime in mass ratio for 100:2 mixes, old 1 day so that the residual acid in phosphogypsum is fully neutralized by unslaked lime; Again this compound is placed in to drying machinery and under 180 DEG C and condition of normal pressure, carries out drying and dehydrating and process 1h, obtain dehydrated phosphogypsum-neutralization with lime material;
(2) batching: take dehydrated phosphogypsum-neutralization with lime material, yellow sand, 2 kinds of shared mass percents of raw material are: 70% dehydrated phosphogypsum-neutralization with lime material, 30% yellow sand, drop in agitator and be uniformly mixed, make admixtion;
(3) water mixing is stirred: to admixture water in admixtion, the mass ratio of admixtion and watering quantity is 100:18, is uniformly mixed fully, obtains water mixing admixtion;
(4) compression moulding: by water mixing admixtion cloth in brick pressing machine, the compression moulding adobe of making a living under 8MPa pressure;
(5) soaked aquation: life adobe is placed in to room temperature water and soaks 0.5h, make aquation adobe;
(6) seasoning: by aquation adobe dry 7 days under field conditions (factors), make baking-free ardealite brick product.
(taking compression moulding time start to calculate) intensity test value was 26.6MPa 7 days of the prepared baking-free ardealite brick product of the present embodiment, met the standard-required of the 25MPa ultimate compression strength of JC/T422-2007 " non-sintering rubbish tailing-bricks " (grade MU25).
Method technique provided by the invention is simple as seen from the above embodiment, do not need to mix cement or tackiness agent, cost is low, and the baking-free ardealite brick intensity of preparation is high, meet the standard-required of the normal intensity grade MU25 of JC/T422-2007 " non-sintering rubbish tailing-bricks ", thereby be suitable for suitability for industrialized production.
Be understandable that, above embodiment is only used to principle of the present invention is described and the illustrative embodiments that adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.

Claims (4)

1. a production technique for the high content phosphor-gypsum baking-free bricks of high strength, is characterized in that comprising the following steps:
(1) raw materials pretreatment: phosphogypsum is mixed with unslaked lime, obtain compound, after old 1 day, compound is placed under drying machinery condition of normal pressure in 180 DEG C of dry dehydrated phosphogypsum-neutralization with lime material that obtain;
(2) batching: take in proportion dehydrated phosphogypsum-neutralization with lime material and yellow sand, drop in agitator and be uniformly mixed, make admixtion, in admixtion, the quality proportioning of each component is: dehydrated phosphogypsum-neutralization with lime material of 70~90%, 10~30% yellow sand;
(3) water mixing is stirred: in admixtion, add water, the mass ratio of admixtion and water is 100:18~25, is fully uniformly mixed and obtains water mixing admixtion;
(4) compression moulding: water mixing admixtion is inserted in brick pressing machine, and compression moulding under 8~12MPa pressure, obtains raw adobe;
(5) soaked aquation: under room temperature, life adobe is placed in to water and soaks 0.5~2h, obtain aquation adobe;
(6) dry: by aquation adobe dry 7 days under field conditions (factors), to make the high content phosphor-gypsum baking-free bricks of high strength.
2. the production technique of the high content phosphor-gypsum baking-free bricks of high strength according to claim 1, is characterized in that: step (1) described time of drying is 1h.
3. the production technique of the high content phosphor-gypsum baking-free bricks of high strength according to claim 1 and 2, is characterized in that: the described phosphogypsum of step (1) is 100:2 with Lime Quality ratio.
4. the production technique of the high content phosphor-gypsum baking-free bricks of high strength according to claim 1, is characterized in that: described yellow sand water ratio≤5% of step (2), sand rain size≤2.36mm.
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CN104310930A (en) * 2014-09-26 2015-01-28 中国地质大学(武汉) Production process of unfired building ceramic
CN105645897A (en) * 2015-12-04 2016-06-08 山东高唐天齐液压机械有限公司 Green and environment-friendly baking-free brick and preparation method thereof

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CN110452557A (en) * 2019-07-10 2019-11-15 贵州贵诚舜源环保科技有限公司 A kind of application of Phosphogypsum-modifymethod method and modified ardealite

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CN102775118A (en) * 2012-08-15 2012-11-14 四川省富侨工业有限公司 Method for producing baking-free brick by doping phosphogypsum and fly ash

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CN105645897A (en) * 2015-12-04 2016-06-08 山东高唐天齐液压机械有限公司 Green and environment-friendly baking-free brick and preparation method thereof

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