CN1539780A - Method for producing white and color silicate cement from sinter of yellow phosphorus - Google Patents

Abstract

A process for preparing the white or color Portland cement from the cinder generated during production of yellow phosphours is disclosed.

Description

The method of yellow phosphorus slag production white and colored portland cement

The present invention relates to fusion, the waste residue of molten slag, the used heat utilization of being discharged in the Industrial processes such as yellow phosphorus and pig iron smelting, is a technological project that realizes the industrial high temperature slag energy and comprehensive utilization of resources.

Utilize method of the present invention, can produce that all kinds of cement, particularly added value are higher, market outlook good, have the white and the colored portland cement series product that beautify and adorn function with industrial high temperature slags such as yellow phosphorus and pig iron smeltings.

This specification sheets will be embodiment with yellow phosphorus slag production white and colored portland cement, and just the technical problem of the ultimate principle of invention, required solution, concrete solution and flexible technology process are made detailed description.

Phosphorus production practitioner knows: 1 ton of finished phosphorus of every production just will produce 8～10 tons of temperature up to 1400 degrees centigrade, heat load is fusion, the liquid state waste slag of 48.3 ten thousand kilocalories per ton and reaction end gas 3000 standard cubic meter that contain 80～90% flammable CO.

For a long time, because technology limitation, phosphorus production enterprise can only follow the backward technology of tradition of shrend granulation cooling high-temperature slag is handled, no matter the slag heat load runs off in vain, has also caused the waste of water resources and the pollution of ecotope; And; except that being used to produce Portland cement, slag cement, clinker-free cement as the cement admixture or being used to produce other low value-added building material product (as: building brick, mix and doubt native member etc.), there is not other considerable utility value through the yellow phosphorus granulation waste residue of Water Quenching again.Therefore, the yellow phosphorus Water Quenching Slag can only even be given for free to cement or other building materials manufacturer and use with cheap sell at competitive.

The waste of the energy that treatment process that above-mentioned yellow phosphorus slag tradition falls behind and utilization of resources approach are caused, the pollution of ecotope and industrial residue added value low seriously restricted the raising of development that China phosphorus production enterprise produces and competitive power, become the big bottleneck that China's yellow phosphorus industry is realized Sustainable development.

But then, Cement industry also is the conventional industries that energy consumption is huge.Single with regard to the grog firing process, 1 ton of cement clinker of every calcination just needs to consume the heat (level that production technique that this is still comparatively advanced and device can reach) about 900,000 kilocalories; And cement is the huge building material product of a kind of consumption, and for a long time, various places are for producing the cement mining of cutting into a mountain everywhere, and the destruction of causing natural resources and natural landscape is very much painful.

Though at present Cement industry is mixed all types of industries granulation waste residue among the grog as mixing material, has realized the utilization of resources to a certain extent, this fusion utilization can't realize the recycling to the industrial slag heat load.

And the huge energy dissipation that the industrial slag shrend is caused is obvious to all.

Thus, the contriver has to recognize: if realize that yellow phosphorus and pig iron smelting etc. produce slag industry and combine more closely with cement production industry, replenish raw material and heat energy such as a part of composition correction with the fusion industrial residue, directly calcination goes out cement clinker, all will be a Gospel in state in the people:

1, realized the recycling of industrial high temperature molten slag institute heat load;

2, realized producing the utilization of slag industrial residue resource;

3, gained cement has the higher quality assurance, and non-slag cement can reach;

4, reduce manufacture of cement ore extraction amount, ensure natural landscape and water and soil safety;

5,, will therefore significantly improve so produce the economic benefit of slag industry because gained cement caters to industrial production and slag composition characteristics thereof, and production cost is lower.

And for producing the very huge China's phosphorus production industry of the quantity of slag, realize the slag energy and resource common utilization, realize the perfect adaptation of it and Cement industry then seeming more urgent.

It is a kind of in that former batching ratio and processing condition do not make any changes, guarantee to put before former order of phosphorus production and the quality product to phosphorus production that the present invention just provides, realize that phosphorus production waste residue, used heat all utilize, and produce the processing method with flexible production ability of cement products.

Briefly, that is: based on the chemical constitution of yellow phosphorus slag, be foundation, bring into play Fe in the yellow phosphorus slag with the chemical reaction mechanism that generates white portland cement clinker ₂O ₃Less and the phosphorus production of content possesses the advantage of ready-made CO combustion gas, adds Al when the uncolled crystallization still of yellow phosphorus deslagging, slag ₂O ₃, CaO and mineralizer and replenish a part of heat by the CO combustion gas after; reaction generates white portland cement fusion grog; through air-flow micronize, the sorting of grog whiteness, tinting pigment preparation, combined grinding, finished product warehouse-in and rich iron melt is settlement separate and flexible technology process such as spray bleaching, production is produced again

The product added value is higher, market outlook good, have the white and the colored portland cement that beautify and adorn function; And on this basis, improve technology and install the adaptive faculty that situations such as the phosphorus production characteristics and the market requirement are changed, the production needs that satisfy other type cement, reach the common utilization that allows the yellow phosphorus slag turn waste into wealth, make the best use of everything, realize the phosphorus production energy and resource, the final purpose that improves the phosphorus production business economic benefit and the market competitiveness.

At first, consist of example, make an explanation with regard to the ultimate principle of this invention and the guiding theory of technological design with yellow phosphorus slag oxide compound:

The yellow phosphorus slag is a kind of acidity (SiO ₂/ CaO) be about 0.8, Al ₂O ₃Content is than SiO ₂Be low alkaline low activity slag, its important oxide compound composition is roughly (weight percent):

CaO 48％

SiO ₂ 38％

Al ₂ O ₃ 5％

Fe ₂O ₃ 1.2％

After the high-temperature slag shrend, will form with CaSiO ₃And CaSi ₂O ₇Canescence crystal grain for major ingredient.

With respect to producing cement products, the most outstanding characteristics of yellow phosphorus slag are:

(1) SiO ₂Content is higher, so it relatively is fit to produce silicate-type cement;

(2) Fe ₂O ₃Content is less, so it relatively is fit to calcining white cement grog, and then produces and caters to the various whites and the colored portland cement of market demand.

Therefore, the present invention has taked that the production added value is higher, good market prospect, has had and beautify with the white and the colored portland cement of the function of adoring and take into account the prioritization scheme that other type manufacture of cement needs:

---for improving the slag activity, adjusting oxide compound rate value, just should when the uncolled crystallization still of yellow phosphorus deslagging, slag, in slag per ton, add oxide composition correction material Al to satisfy manufacture of cement needs (SM=3～4) ₂O ₃And Fe ₂O ₃Amount to 60～70 kilograms;

---because the shade of cement clinker depends on Fe in the grog ₂O ₃Content is Fe in the performance yellow phosphorus slag ₂O ₃Higher white and the colored portland cement of advantage, production added value that content is less, elite selecting only added Al in slag per ton ₂O ₃The prioritization scheme that aluminium matter composition correction material is 60～70 kilograms;

---add Al with yellow phosphorus slag per ton ₂O ₃Total aluminum oxide quantity (110～120 kg/ton slag) is the material balance benchmark and deducts the CaO amount (480 kilograms of/ton slags) that the yellow phosphorus slag originally just contains behind the composition correction material, can learn: produce cement clinker, also should in slag per ton, add CaO600～700 kilogram.

By above-mentioned Al ₂O ₃And the adding of CaO, the essence variation has just taken place in the oxide composition of the former alkaline low activity slag of being discharged by the phosphorus production device.Add each main oxides composition of back and be roughly (weight percent):

CaO 65.8％

SiO ₂ 22.2％

Al ₂O ₃ 6.7％

Fe ₂O ₃ 0.7％

Its rate value is: KH=0.9; SM=3; IM=9.6

This monoxide is formed the Chemical Composition needs that just satisfied the white portland cement clinker formation reaction substantially.On this basis, heat energy by the inherent CO of phosphorus production combustion gas own replenishes the foundation that reaches other reaction conditions again, the series of chemical that white portland cement clinker generates just can take place in each oxide compound, finally generating with silicate, aluminosilicate is the white portland cement clinker of major ingredient, and its essential mineral composition is roughly (weight percent):

Silicate minerals is more than 75%

3Cao·Al ₂ O ₃ 16～20％

4CaO·Al ₂O ₃·Fe ₂O ₃ 1.5～2.5％

Though, the tetracalcium aluminoferrite content that influences white cement whiteness quality in the above-mentioned grog component is still higher, but the present invention has taked a series of corresponding measures, this problem has been proposed special concrete solution (specification sheets hereinafter will be made detailed description), and this defective can remedy fully.

Certainly, be to exist some to be unfavorable for the objectionable impurities of white portland cement clinker quality in the yellow phosphorus slag chemical constitution.But the content of these oxious components in slag is less, and by after adding composition and calcining out cement clinker, their content in grog is just very little especially, and (as: MgO is 0.8%; P ₂O ₅Be 0.9%), well below national standard about upper control limit to objectionable impurities in the cement clinker, therefore totally unnecessary worry.

Like this, produce the material conditions and the heat energy condition of white portland cement clinker is just set up with the yellow phosphorus slag, under the technology of flexible production flow process of the present invention was supported, production white and colored portland cement and the invention target of making the best use of everything, take into account other type manufacture of cement just can realize.

Certainly, by adding suitable composition correction material, the yellow phosphorus slag is carried out modified modification, satisfies the chemical reaction composition condition of particular type cement clinker generation and replenishes partial heat energy and then reaction generation special cement grog this basic principle and method, be not limited to produce white and colored portland cement: by adjustment to interpolation type of feed and quantity, utilize this ultimate principle and method, project implementation enterprise can produce the cement products of other type according to the s own situation and the cement market requirement of phosphorus production fully:

Such as, project implementation enterprise removes can be by CaO and Al ₂O ₃, Fe ₂O ₃Common adding [CaO 600～the 700kg of composition correction material; Al ₂O ₃15～20kg; Fe ₂O ₃45～50kg (in 1 ton of slag)] produce outside the ordinary Portland cement, if market demand can be utilized this ultimate principle and method equally, produce high-alumina cement: a large amount of Al of adding in yellow phosphorus slag per ton ₂O ₃And The addition of C aO and additional abundant heat energy, just can calcine out 6～7 times of high aluminium cement clinkers to former slag weight; It as raw material, then can be produced radiation proof cement (U.S. stone of high aluminium cement clinker admixture boron and gypsum grind), expansive cement (Portland cement 70～75%, high-alumina cement 12～13%, dihydrate gypsum 14～17% grind jointly) and self-stressing cement.

The maximization of its benefit is always pursued in the economic activity of enterprise.

The contriver why with production white and colored portland cement as inventive embodiments, stressed and proposed corresponding solution targetedly, be because white and the colored portland cement added value is higher, it is wide to use, market adaptability has been brought into play phosphorus production institute inherent advantages, the cause that energy consumption and production cost are lower by force simultaneously.Enterprise turns a blind eye to this as for the project implementation, utilize on the contrary this ultimate principle and method production added value lower or even ordinary Portland cement, then be that a kind of and marketable value are seen the improper behavior of runing counter to;

Simultaneously, the contriver does not advocate project implementation enterprise yet and utilizes method production of the present invention and yellow phosphorus slag composition characteristics to greatly differ from each other as the special cement of high-alumina cement and so on for pursuing high added value.Energy consumption will be big, production cost is high because this will cause, and also abandon Fe in the yellow phosphorus slag simultaneously ₂O ₃Content is less, the rare advantage of production white and colored portland cement.

Therefore, at phosphorus production practical situation and Protean cement market trends, the contriver is when proposing to have a whole set of processing method flow process and device design of flexible production ability, also submit to project implementation enterprise to take the industrial slag utilization of resources ruleization of " serving as theme with the colored portland cement series product of producing white and satisfying different customer demands; make the best use of everything, take into account other type manufacture of cement ", maximize favourable factors and minimize unfavourable ones, realize fully project implementation maximizing the benefits.

The above, be the ultimate principle of yellow phosphorus slag production white and colored portland cement and flexible technology process and device design fundamental guiding ideology, be that the present technique project is able in industrial utilization and popularization and obtains the basic assurance of preferable economic benefit.

On the basis of the ultimate principle of foregoing invention, set up the white portland cement clinker generation chemical reaction condition, calcine out the white portland cement clinker of requirement up to specification, and then produce white and the colored portland cement series product that satisfy client's different needs, reach fundamental guiding ideology and marketable value that phosphorus production waste residue, used heat all utilized, demonstrated fully the present invention, just must solve the technical problem of following all many-sides:

(1) the additional problem of efficiently utilizing that reaches of heat

According to yellow phosphorus slag Chemical Composition characteristics, react the generation white portland cement clinker, just must in slag, add a large amount of Al ₂O ₃, CaO (total amount is 660～770 kilograms of/ton slags) and part mineralizer.Thereby the system temperature declined to a great extent and causes the grog formation reaction to carry out after this will cause raw material to add.So it is the key issue of setting up and keep the temperature condition (more than 1600 ℃) of cement clinker formation reaction that grog is generated effectively replenishing of institute's heat requirement; Simultaneously, be save energy, also should realize efficient utilization supplemental heat source.

(2) mixing of material and reaction generation problem

Since the slag of discharging from the phosphorus production device be high temperature and liquid state and the raw material that adds to slag is to be solid state.Therefore, Gu how to realize liquid---the uniform mixing of two-phase material and guarantee the required time of white portland cement clinker formation reaction, facilitate the grog generation chemical reaction fully, just become the crux technical problem that the present invention must solve.

(3) micronize of grog, raising grindability problem

The higher invention target of the fundamental characteristics of yellow phosphorus slag and production higher quality white portland cement clinker has determined necessary employing scorification to carry out the calcination of grog.But this must cause the grog that generated harder, causes very big difficulty for cooled grog grinding.Therefore, must seek a simple way, thereby so that the rapid micronize of fused liquid phase cement clinker, the granularity that reduces to cool off the back grog, the electric power when reducing the grog grinding and devices consume reduce production and cost of equipment maintenance;

Simultaneously; realize the grog micronize; also helping on technology to guarantee this processing method flow process especially about white portland cement clinker being carried out the whiteness sorting, realize product seriation, expanding the target call of manufacture of cement kind, is that the important technology that the present invention's process unit possesses the flexible production ability guarantees.

(4) formation of color and product seriation problem

Because Fe in the yellow phosphorus slag ₂O ₃Content will be inevitably in the yellow phosphorus actual production process with lot of unstable factors such as production batching, material quality and process control condition fluctuate (for working condition is not very good producer, and this problem will be more outstanding).This will have a strong impact on the whiteness grade and the stability of gained white portland cement clinker.How according to the situation of this outwardness, in operations such as raw material adding, grog grinding, color formation, adapted to, expanded the manufacture of cement kind, and even, just become the practical problems that the present invention improves the market adaptability, realizes the required solution of project implementation maximizing the benefits to improve phosphorus slag utilization ratio, the rate of reducing the number of rejects and seconds, realize the product seriation under lower cost of white and other cement type of colored portland cement, to satisfy the Protean cement market requirement.

(5) the bleaching problem of rich iron grog

Since behind the raw materials such as yellow phosphorus slag adding composition correction, its Fe ₂O ₃C in content still higher (about content 0.7%), the grog that generated ₄AF mineral content excessive (about 2%), this will be difficult to form the higher white portland cement clinker of whiteness quality; Moreover, owing to unavoidably also contain micro-irony in raw material such as the composition correction that added and the mineralizer.Therefore, adopt an effective measure,, whiteness inferior quality grog higher to iron-holder bleached, and is to improve and the important technology security problem of the necessary solution of stable white Portland clinker whiteness quality institute.

The present invention consists of the basis, is foundation with the chemical reaction mechanism that generates white portland cement clinker with yellow phosphorus high-temperature slag oxide compound, maximize favourable factors and minimize unfavourable ones, maneuverability, to produce white and the colored portland cement series product are served as theme, make the best use of everything, take into account other type Cement Production, tightly center on the technical problem of above-mentioned five aspects, proposed solution and a whole set of processing method flow process that possesses the flexible production ability and device design, opened up the new ways that phosphorus production waste residue, used heat all utilize at these problems.

Below, in conjunction with Figure of description, just the present invention's process of flexible production process is made detailed description.

In the Figure of description:

Fig. 1, flexible technology Principle of Process figure;

Gu Fig. 2, liquid---batch mixing structure of reactor synoptic diagram;

Fig. 3, batch mixing plate runner distribute and mixing principle figure;

Fig. 4, time-delay separating tank structural representation;

Fig. 5, the cheap facility synoptic diagram that substitutes;

Fig. 6, combustion gas, material spray fusing device structure principle chart.

The present invention's flexible technology process by slag store buffering, raw material compounding, grinding oven dry, batch mixing reaction, time-delay reaction, air-flow micronize, the sorting of grog whiteness, pigment preparation, combined grinding, finished product is put in storage and (referring to Figure of description 1---flexible technology Principle of Process figure) formed in the concrete operations unit such as settlement separate and spray bleaching of rich iron melt:

(1), slag is stored buffering

The deslagging operation of phosphorus production is step (arranged once, carried out approximately 20 minutes at every turn in general 4～6 hours) mostly, and the deslagging crest certainly will cause very big flow pressure to cement production.For inferior, the present invention has at first taked the yellow phosphorus slag is stored the measure at buffering, the balance flow paddy peak that deslagging causes at intermittence.That is: slag is set and stores surge tank (1), with intermittently, concentrate the yellow phosphorus slag of discharging to remove ferrophosphorus and nut coke after pipe special is sent into slag stores in the surge tank (1) and under CO combustion gas insulation and store.Because the restriction that engineering design is stored surge tank discharging unit time flow to slag, the every row's primary slag of phosphorus production device just can be for surge tank continuous blow-down 4～6 hours.Like this, just realized with the yellow phosphorus slag produce cement products the explained hereafter continuity, alleviated yellow phosphorus deslagging crest to process unit potential flow pressure;

With respect to the cement clinker formation reaction, because SiO in the yellow phosphorus slag ₂Content big (38%) and CaO content less (48%) in storage surge time of 4～6 hours, according to the chemical reaction mechanism of cement clinker generations, still do not have generation C ₃The material conditions of S.Therefore, do not exist owing to high temperature storage, the long C of causing of calcination time ₃S forms the problem that thick and round crystal influences the cement clinker quality.

(2), add the compounding of raw material

Form and the requirement of manufacture of cement kind according to yellow phosphorus slag oxide compound, select CaO, Al ₂O ₃And other composition correction material, mineralizer and blended process in addition, be raw material compounding operation.

Major equipment is by CaO (lime) storehouse (2), Al ₂O ₃(alumina) storehouse (3), mineralizer storehouse (4), standby former feed bin (5), rotary conveyor (6), blending bunker compositions such as (7);

Produce white portland cement to adding the requirement [Al of composition correction material according to the yellow phosphorus slag ₂O ₃60～70 kilograms, CaO600～700 kilogram (in 1 ton of yellow phosphorus slag)], it is standby to be transported to blending bunker (7) by rotary conveyor (6) after the weighing respectively;

Installing mineralizer storehouse (4) purpose additional is to use mineralizer selectively, and the mineral that quicken cement clinker form and reduce liquid phase viscosity.For improving white portland cement clinker whiteness quality, can select to contain BaCO ₃Or BaSO ₄The composite mineralizer of composition;

The purpose of standby former feed bin (5) is set, be to make process unit possess the flexible production ability, to adapt to the cement market demand: project implementation enterprise can change and the cement market requirement according to yellow phosphorus slag composition, adjust the composition correction material type added by standby former feed bin (5), the cement clinker of calcining other type (or adds tinting pigment on this basis, directly calcine the colored cement grog), change and the Protean cement market requirement to adapt to enterprise self phosphorus production situation.

(3), grinding oven dry

The composition correction material that adds for making, mineralizer can with yellow phosphorus slag uniform mixing, at first must carry out grinding to these solid-state interpolation raw materials, this operation is carried out in equipment (8).In order to improve liquid---Gu material temperature is added in the calorific value utilising efficiency of the used CO combustion gas of follow-up workshop section such as batch mixing reaction and time-delay separation and moisture, the raising of removing in composition correction material and the mineralizer, equipment (8) should have grinding, two kinds of functions of oven dry: when solid material, mineralizer are carried out grinding, utilizing the follow-up CO of workshop section combustion exhaust that solid is added raw material dries and heats last gas (CO ₂And water vapor) extracts emptying out by induced draft fan;

Raw material such as powdery composition correction after grinding and oven dry, the heating and mineralizer are discharged back and the yellow phosphorus slag of storing surge tank (1) from slag evenly collocation and enter jointly in the batch mixing reactor (9) and carry out liquid---the uniform mixing of solid-phase material and the initial reaction that cement clinker generates to scale by grinding dryer (8);

With slag liquid level change in yellow phosphorus deslagging, the slag storage surge tank (1) periodically variable situation appears for adapting to yellow phosphorus slag unit time flow, grinding dryer (8) should be able to be realized speed adjustment, to guarantee liquid---and solid-phase material blend proportion, assurance cement clinker quality;

For guaranteeing white portland cement clinker whiteness quality, grinding dryer (8) preferably selects to produce the grinding and the drying plant of white portland cement special use.

(4) Gu, liquid---mix and initial reaction

Yellow phosphorus slag after removing contained ferrophosphorus and being mingled with nut coke after slag is stored surge tank (1) the unit time flow is flowed out in accordance with regulations, with from grinding dryer (8) Gu powdery composition correction material, mineralizer be the ratio collocation and together enter liquid---in the mixing reactor (9).Liquid---solid matter is flowing in specially designed runner, through repeatedly intersecting, separate the effect that mixes mutually that reaches; With this simultaneously, the a plurality of CO burners that are installed on the reactor cap constantly replenish heat energy to reactive material, cause the reaction system to keep sufficiently high temperature of reaction (more than 1600 degrees centigrade) and fusion or semi-melting state, discharge reactor (9) at last, enter in the time-delay separating tank (10), carry out next step operation;

Slag mixes in this equipment with raw material, mineralizers such as composition corrections and time of reacting only is 1～2 fen kind, therefore, the mixing and the heating of liquid---Gu the main purpose of batch mixing reactor (9) is liquid---solid-phase material also makes the material fusion of trying one's best, and the cement clinker formation reaction of being carried out also only is initial reaction;

Gu liquid---batch mixing reactor (9) is a high temperature mixing, stirring and initial reaction equipment.Its structure (referring to Figure of description 2---liquid-solid batch mixing structure of reactor synoptic diagram, among the figure: 37-supporting base, 38-metal casing, 39-thermal insulation layer, 40-batch mixing plate, 41-adiabatic cover plate, 42-CO burner, 43-opening for feed, 44-discharge port, 45-outlet port) is made up of support plinth, metal shell, thermal insulating warm-keeping layer, batch mixing plate, adiabatic cover plate and a plurality of CO burners, charging and discharging mouth and the outlet port etc. that are mounted thereon.Its reactor bottom surface tilts at an angle, is convenient to flow of melt; Its core component---batch mixing plate be one parallel with the reactor bottom surface, tilt to place and dig by two groups of melt parallel fluid channels of level crossing, splice, build part by mixing and shrink the high temperature material that two functional sections form.Because the mutual intersection of two groups of parallel slag runners (referring to Figure of description 3---the batch mixing plate runner distributes and mixing principle figure, among the figure: 46-A organizes parallel fluid channels, 47-B organizes parallel fluid channels, 48-mixing section, 49-contraction section, 50-intersection point, 51-margin plate), melt is flowed downward in the mixing section that margin plate is parallel to each other take place in the process repeatedly to intersect, bump, mix isolating again stirring and melange effect, cause raw materials such as molten slag and the correction of powdered composition, mineralizer constantly rolls, stir, interpenetrate, diffusion and heat transfer, and temperature constantly raises under CO combustion gas heat energy replenishes, liquid---interpenetrate between solid matter, the effect of diffusion is constantly strengthened, and finally is fusion or semi-melting state and flows into after contraction section converges in time-delay separating tank (10) and carry out next step operation;

From the yellow phosphorus electric furnace exhaust gas cleaner, its thermal power should be able to satisfy arts demand to additional heat with the CO combustion gas;

[improve the heating efficiency problem of CO combustion gas about using combustion gas material spray fusing device, will be described in the back] to material

The waste gas that the CO burning produces enters in the grinding dryer (8) after being discharged by venting port, to realize oven dry and the heating to composition correction material, mineralizer, reaches the purpose that improves CO calorific value utilising efficiency.

(5) time-delay reaction

By liquid---Gu the melt that batch mixing reactor (9) is discharged is because of reaction times deficiency (1～2 minute condition of high temperature time), and the cement clinker formation reaction is still insufficient.So, it to be sent in the time-delay separating tank (10), and heat once more, heat up and keep high temperature and fusion time about 15 minutes with the CO combustion gas, to guarantee the intensity quality and the flowability of gained cement clinker, one of effect of Here it is time-delay separating tank (10);

[, will be described in the back] about the settlement separate effect of time-delay separating tank (10) to rich iron melt

Suitably the reaction times (about 15 minute) of minimizing melt in time-delay separating tank (10) is owing to burning clinker of cement temperature higher (more than 1600 ℃) and is in complete molten state, as overlong time, and C in the grog that will cause generating ₃The S mineral composition forms thick and crystal circle, thereby influences the grog quality;

The CO burner that plays the effect of heating is installed on tank deck, its with gas come from the purifying exhausting gas of yellow phosphorus device equally, the waste gas that produced enters grinding dryer (8) equally, powder raw material, mineralizer are dried and are heated;

Because yellow phosphorus slag temperature is more than 1400 degrees centigrade, heat load is up to 48.3 ten thousand kilocalorie/tons, and, cement clinker essential mineral composition C ₃The formation reaction of S is little thermo-negative reaction.So, only needing to replenish the part heat and just can calcine out the fused cement clinker, this also just equals to have realized the recycling to yellow phosphorus slag heat load.

(6) air-flow micronize

For the electric power and the devices consume that reduce grog cooling back powder-grinding process, on technology, guarantee to white portland cement the whiteness sorting, set up the flexible production ability of process unit; the present invention has selected to utilize high pressure draft to pass through pneumatic atomizer (12) especially the cement melt has been carried out micronize: when liquid cement clinker of discharging when the high-order discharge gate (11) of time-delay separating tank (10) and high pressure draft meet at the nozzle place of airflow atomizing device (12); the cement melt just is subjected to the intense impact of high pressure draft, is crashed to pieces, dispels and become fine particle.This has created condition not only for the grog grinding, and has realized the chilling to the cement melt, also provides technology ensuring for cement clinker whiteness sorting in the workshop section of back simultaneously;

The used high pressure draft of pneumatic atomizer (12) can be the high-pressure air that is produced by air compression plant, also can be the higher industrial steam of pressure;

Fused cement grog air-flow micronize when operation, guarantee its heat quick transfer, prevent to bond again, this process is finished by cooling unit (13).The pressure cooling of mechanical air supply formula be can adopt, naturally cooling or water spray cooling also can be taked;

For reclaiming, transform and utilize fused cement grog heat load (melt heat load per ton is about 500,000 kilocalories), avoid thermal pollution, save energy, reducing production costs, contriver's recommendations enforcement enterprise adopts an application for a patent for invention that is called " recovery of yellow phosphorus waste slag heat load and reaction end gas thermal value and method of comprehensive utilization ", and (application number: the processing method 03101365.1) reclaims, transforms and utilize the fused cement heat load.Simultaneously, since the process unit of foregoing invention in " tower boiler " internal system be full of and realizes the pressure heat transfer cycle be CO ₂Therefore gas can make cement melt efficient heat transfer mode with fluidization of solid in the environment of secluding air realize chilling.This all will benefit to the assurance of clinker strength quality and the raising of whiteness of white cement clinker grade.

(7) the whiteness sorting of grog

For improving the adaptive faculty of processing method flow process to the phosphorus production practical situation and the cement market requirement; realize white and colored portland cement and other product seriation of type cement under lower cost; the present invention utilizes rotary conveyor (14); whiteness sorting mechanism (15); classification work in-process storehouses (16); realization is to the classification warehousing of different whiteness grade cement clinkers: according to the difference of the apparent whiteness of cement clinker after the micronize; handle whiteness sorting mechanism (15) and go up corresponding spade blocking apparatus; grog is fallen respectively after rotary conveyor (14) interception and deposit in the corresponding classification work in-process storehouse (16); thereby realized classification warehousing, to adapt to owing to yellow phosphorus slag Fe to different whiteness grade cement clinkers ₂O ₃Factor such as content and the practical situation of the grog whiteness grade fluctuation that causes;

The available manual maneuvering of sorting mechanism (15), but preferably adopt the measure of the automatic sorting of photoelectricity: with the powdery grog on the stabilized light source irradiation rotary conveyor (14), according to the gained intensity of reflected light and be converted into electrical signal and go to control sorting mechanism (15) action, reach the purpose of the automatic sorting of photoelectricity;

Work in-process storehouse (16) is made up of the corresponding a plurality of warehouses of pre-sorting whiteness number of levels, and the higher storehouse of whiteness grade will be arranged at the end to the greatest extent of rotary conveyor (14), prevents that the grog of higher whiteness grade is subjected to the pollution of lower grade grog.Also to prevent to accept when returning the situation that the whereabouts grog causes sorting to lose efficacy simultaneously and take place, therefore will carry out the covering encapsulation process returning Pi Lian because of belt;

Work in-process storehouse (16) should possess big volume, and the enterprise bigger for output can replace with the circle storehouse respectively, to prolong the grog shelf-time, to improve grog whiteness grade.

(8) pigment preparation

The pigment preparation is exactly according to the grog whiteness grade and the cement market requirement, prepares various tinting pigments, retardant and other cement additive selectively, so that grind the finished cement of white and colored portland cement or other type, its preparation principle is:

A, for the high cement clinker of whiteness, just do not allocate pigment into, only mix high-quality gypsum and other painted extremely shallow mixing material, the high gear time white portland cement that the production whiteness is the highest, added value is the highest, use in extraordinary occasion;

B, for the higher cement clinker of whiteness, satisfy the white cement that medium retaining time requires or the more shallow various colored cements of color of client's needs with regard to the production whiteness;

C, general for whiteness, the cement clinker that the retaining whiteness requires in being slightly poorer than can be prepared the darker slightly colored portland cement of color;

D, for the relatively poor cement clinker of whiteness, can be according to the market requirement, the painted colored cement that grinds color the darkest (as black, brown etc.); Also can be not with painted, as the raw material of other type special cement (as radiation proof cement, expansive cement etc.) of producing the achromatization requirement; Put goods on the market as ordinary Portland cement, mixed cement after more directly admixture cement additive, retardant grind, this is the simplest, direct treatment process.

In a word, the preparation principle is: pursue benefit, make the best use of everything, draw back retaining, cater to market;

These preparation work are coagulated storehouse (17), blended material feed bin (18), various tinting pigments storehouse (19), lay-by material storehouse (20), rotary conveyor (21), blending bunker major equipments such as (22) by slow agent and are born.It is standby that the pigment for preparing as required, retardant and various mixing material are delivered to blending bunker (22) by rotary conveyor (21);

Equally, for making technology possess the flexible production ability, in order to the cement type (as radiation proof cement, expansive cement etc.) of other type outside project implementation enterprise production white and the colored portland cement, this operation also is provided with lay-by material storehouse (20), to satisfy the flexible production needs;

The production method of aforesaid colored portland cement is only for mixing, mix the indirect production method of formula., its slag Fe better for working condition ₂O ₃The project implementation enterprise of stable content also can adopt the production method of the colored grog of direct calcining: add metal oxide (as Cr in standby former feed bin (5) ₂O ₃, CoO, Mn ₂O ₃Deng) be tinting material, after drying, Gu enter liquid jointly with other raw material and yellow phosphorus slag---in batch mixing reactor (9) and the time-delay separating tank (10), directly calcine the colored cement grog.But at this moment need CO combustion position in reactor (9) and the time-delay separating tank (10) is controlled, adjust the clinker burning atmosphere in reactor (9) and the time-delay separating tank (10), so that obtain the colory colored portland cement grog of object color component.

(9) combined grinding

The white portland cement clinker of being classified, storing enters the grinding that carries out particular fineness in the milling equipment (25) jointly after lift (24) promotes the back and the corresponding pigment of preparing in advance according to the production purpose from blending bunker (22), retardant and other mixing material mix by preset proportion and operates by sending into rotary conveyor (23) respectively by the production purpose in classification work in-process storehouses (16) and sending to, and this operation is combined grinding;

Because undertaken spray particlesization by high pressure draft before the cement clinker cooling, granulation grog particle is less, so the grinding pressure of finished product is very not big;

For guaranteeing particularly high-grade white of product and colored cement color quality, many covers (at least two covers) grinding and feed device thereof should be set.Wherein a cover should be specifically designed to and produce high-grade white and colored portland cement: its grinding machine should adopt production white and colored portland cement special use, be liner plate, be the grinding machine of grinding element with siliceous cobble with pottery, grouan or high-quality wear resisting steel.

(10) finished product warehouse-in

Should classify after the finished cement of white and colored portland cement and other kind grinds metering packing and separated deposit are avoided crossed contamination.Stockyard should possess enough capacity, assurance inspection after construction required time, and the product strength stand the test can be dispatched from the factory;

For alleviating the warehousing pressure of finished goods warehouse, can take the measure of " product is subscribed, produced according to single ", this also is the big advantage that " flexible production line " possessed.

Settlement separate and the spray bleaching of (11) rich iron melt

At " technical problem 5 ", make to contain C ₄The cement clinker that the AF composition exceeds standard brightens, and at first must solve C in the melt ₄The AF composition separates with other mineral composition, so that significantly alleviate the consumption of the processing pressure of follow-up spray bleaching workshop section, the equipment input that reduces bleachery and bleaching medium.Take all factors into consideration yellow phosphorus slag Fe ₂O ₃C in content (1.2%), the gained grog ₄AF mineral content (about 2%) and the CaO, the Al that are added ₂O ₃And also contain factor such as a small amount of irony in the raw material such as mineralizer, after separating measure adopts, as long as follow-up spray bleaching workshop section treatment capacity reaches 5～10% of fused cement grog total amount, just can satisfy arts demand, handle and needn't all carry out spray bleaching all cement clinkers;

This separate targets is that the principle according to gravity settling is achieved in time-delay separating tank (10): because C in the fused cement grog ₄The proportion of AF is big (molecular weight ratio: C than other mineral composition ₄AF: C ₃A: C ₃S: C ₂S=2.83: 1.56: 1.33: 1), in separating tank (10) relatively in about 15 minutes time of static condition, C ₄AF must be tending towards sedimentation, and makes the C of separating tank (10) bottom ₄AF concentration is higher than far away wherein, top, and Here it is delays time separating tank (10) to C ₄The settlement separate effect of the rich iron melt that AF mineral composition content is bigger;

For further strengthening because of different this gravity settling and the centrifugations that cause of mineral composition proportion, the present invention to the charging of time-delay separating tank (10) taked " funnel " formula " low level charging " measure (referring to Figure of description 4---time-delay separating tank structural representation, among the figure: 52-supporting base, 53-loading hopper, 54-funnel straight tube, 55-heating and melting space, 56-settlement separate space, the high-order relief outlet of 57-poor iron melt, 58-rich iron melt low level relief outlet, 59-venting port, the 60-CO burner, 61-outlet port, 62-opening for feed): " funnel " type structure is adopted in the charging of time-delay separating tank (10), the straight tube straight cutting of " funnel " go into separating tank bottom and with keep certain distance at the bottom of the jar, on the taper bucket of " funnel " is divided into separating tank (10) inside, following two separate space: going up the space is CO combustion gas heating and melting space, bears the material heating and makes abundant fused task; The space of bottom insertion " funnel " straight tube is the time-delay separated space, is used to store melt, prolongation reaction times and realization to C ₄The gravity settling separation of AF mineral composition.For guaranteeing that the melt in the taper bucket flows into the time-delay separated space smoothly through " funnel " straight tube, this top, space should have venting hole and communicate with atmosphere;

When from liquid---when Gu the fusion of batch mixing reactor (9) or semi-melting material enter in the time-delay separating tank (10) by the tank deck opening for feed, at first be subjected to being installed on the heating of the CO burner of tank deck, temperature raises and realize abundant fusion in separating tank heating and melting space, flows into the bottom of time-delay separating tank (10) then through the straight tube of " funnel ".Because C ₄AF proportion is big than other mineralogical composition proportion in the melt, so C ₄AF will be in separating tank (10) bottom deposit; The mineral composition that proportion is lighter (that is: poor iron melt) then " come-up " in the time-delay separated space of separating tank (10), top, and discharge by the high-order discharge gate (11) of time-delay separating tank (10), enter air-flow micronize workshop section and handle;

By settlement separate, C ₄AF concentration rich iron melt big, that influence white portland cement clinker whiteness quality is then discharged by the low level discharge gate (26) of time-delay separating tank (10), enter in the airflow atomizing device (28) at spray bleaching tower (27) top through special pipeline, its spray bleaching operation carried out: high pressure steam with CO gaseous reducing agent chloride solns such as (or) NaCL by steam injecting type sucker (29) the suction port suction and after the convergent divergent channel supercharging, enter pneumatic atomizer (28) jointly.At spraying gun (28) nozzle place, be rich in C what high pressure steam will be met with it ₄The melt of AF composition smashes, breaks up, atomizes simultaneously, the Fe in CO that contains in the steam (or NaCL) and the melt ₂O ₃Produce chemical reaction, generate painted more shallow Fe ₃O ₄, FeO (or has volatile FeCL ₃), because its color more shallow (or the irony composition volatilizees), so reached whitening effect to the cement melt;

For effectively prolonging Fe in CO (or NaCL) and the melt ₂O ₃Contact and reaction times, improve bleaching effect further, the present invention has also taked to be provided with the measure that cover (32) is strengthened in installation especially: strengthening cover is that the shape metal cap is put in loudspeaker expansion, it can be fixed in spray bleaching tower (27) inside, airflow atomizing device (28) is threaded with it, cannot not guarantee looseningly, air tight;

When using muriate such as NaCl, strengthen cover (32) top should draw a delivery pipe that stopping valve is housed, so that the FeCl that the discharging reaction is generated when needing for the bleaching medium ₃Volatile matter;

Owing to adopt spray bleaching technology, not only effectively increased contacting between bleaching medium (muriates such as CO reductive agent or NaCL) and the melt, reaction area, improved bleaching effect, and can make the melt micronize and realize chilling grog;

After falling within bleaching tower (27) bottom under the grog of bleaching, granulation; be subjected to coming from of the cooling effect of the water coolant of cooling-water pump (30) once more by water-cooled heat exchanger (31); the temperature back that descends is discharged by relief outlet, again by rotary conveyor (14) and C from cooling unit (13) ₄The less poor iron cement grog of AF content enters the sorting of grog whiteness together and handles with classification warehousing unit;

After delivering to the cooling tower cooling, the water coolant that absorption grog heat, temperature raise can be recycled;

Steam and CO chloride solns such as (or) NaCL add-on realizes control by valve (33), (34); The exhaust system of spray bleaching tower (27) should install cleaning apparatus (35) additional, and the dirt material after being concentrated, separating returns at the bottom of the tower; If select for use the CO gaseous reducing agent for the bleaching medium, also should install the device of releasing flare (36) additional, allow have neither part nor lot in reduction reaction, unnecessary CO gaseous combustion emptying, avoid CO directly discharging cause pollution to environment;

When selecting for use the CO gaseous reducing agent to be rich iron melt bleaching medium, also must be noted that: before the operation, should at first use steam that air in the tower is fully replaced, and guarantee positive pressure operation all the time; The cement melt liquid level of time-delay separating tank (10) should keep, and forbids that bleaching tower (27) is owing to the situation that no melt in the separating tank (10) sucks air takes place; Before the spray bleaching system shutdown, must close CO suction valve (34) maintaining under the state that melt enters in advance, and continue to feed steam, treat can cut off after emptying flame extinguishes gradually melt and supply with, at last could steam off valve (33), finish shut-down operation.This is the basic security rules that native system is handled when selecting the CO gaseous reducing agent as the bleaching medium for use;

As for selecting which kind of medium that the cement melt is carried out the chemical method bleaching, look the practical situation of cement melt and project implementation enterprise self, grasp flexibly and adjust;

It should be noted that owing to muriates such as NaCl at high temperature volatilize and be exceedingly fast.So, when selecting for use this type of material during medium, should increase the length of strengthening cover (32) as far as possible, to prolong the Fe in muriate such as NaCl and the cement melt as far as possible as bleaching ₂O ₃Being in contact with one another in strengthening the cover shielding, reaction times, prevent that NaCl from escaping because of volatilization too quickly, guarantees bleaching effect;

By above-mentioned with Fe ₂O ₃And the chemical reaction between the CO (or NaCl) is ultimate principle, is nucleus equipment, is the spray bleaching treating processes to rich iron melt of reinforcing process with air-stream spraying, the contact reacts area that improves bleaching medium and cement melt that with spray bleaching tower (27) the overall whiteness quality of white portland cement clinker will significantly improve.This has crucial product retaining and reaches the quality assurance meaning for improving white and colored portland cement product retaining, raising yellow phosphorus slag utilization ratio, reduce scrap rate, improving the economic benefit of the project implementation.So vital subsystem in its formation the present invention's the flexible technology process;

Also it is pointed out that for the still undesirable few part of those whiteness qualities after the spray bleaching art breading rich iron grog inferior, must not mix with the preferable poor iron grog of quality and carry out the whiteness sorting.Tackle its independent warehousing, can be used as the production ordinary Portland cement and (mix because of the not good C of other reason quality ₃S, C ₂S, add gypsum and yellow phosphorus Water Quenching Slag grind jointly form), the raw material of mixed cement, also can be used as produce other special cement raw material (as buy and add high-alumina cement and produce expansive cement, self-stressing cement)---this also is the advantage that the present invention's " process of flexible production " is possessed.

In sum, the present invention combines with cement production industry more closely for realizing phosphorus production industry, produce cement particularly white and colored portland cement with the yellow phosphorus slag, oxide compound with the yellow phosphorus slag consists of the basis, chemical reaction mechanism with the white portland cement clinker generation is a foundation, maximize favourable factors and minimize unfavourable ones, make the best use of everything, be close to the market, flexible, create yellow phosphorus slag production white and satisfy the processing method flow process with flexible production ability of various colored portland cements or other type cement of different customer demands, solve many important technological problems, opened up the phosphorus production waste residue, the new way that used heat all utilizes.

Through measuring and calculating, adopt described processing method of the present invention, yellow phosphorus slag per ton can react 1.7～1.9 tons of cement clinkers that generate different whiteness grades; Just in 8～10 tons of slags of finished phosphorus by-product per ton, after the present technique project implementation, yellow phosphorus per ton amounts to by-product white and colored portland cement or other type cement products to 16～20 tons, therefore has higher economic value.

It needs to be noted, as the method that various cement are produced in a kind of industrial residue, used heat comprehensive utilization, the present invention and described processing method flow process with flexible production ability also are specially adapted to pig iron smelting or other produces the energy of slag industry and the comprehensive utilization of resource.

Only be example with the blast furnace slag: the physical property of blast furnace slag and oxide compound thereof are formed and the yellow phosphorus slag there is no essential distinction, and its important oxide compound composition is roughly (weight percent): CaO42～44%, SiO ₂36～41%, Al ₂O ₃8～14%, Fe ₂O ₃1～2%, these Chemical Composition are formed close with the yellow phosphorus slag.So, take method of the present invention and process of flexible production flow process and device, can realize common utilization fully, produce the cement products of the particular type of catering to the cement market demand, to satisfy the pursuit of enterprise the economic benefit and the market competitiveness to the blast furnace slag energy and resource.

So the present invention possesses comparatively wide utilization field is arranged.

On the basis of above-mentioned flexible technology method flow, the contriver also considers: when stating technological project on the implementation, if project implementation enterprise can suit measures to local conditions, substitute even save equipment component in the technical process with cheap facility, will effectively reduce the project investment cost, this to the project implementation and economic benefit thereof with of great advantage.

Below, only being built on higher topographical such as the hillside with production equipments such as yellow phosphorus or pig iron smeltings is example, propose to utilize in this case the hillside, suit measures to local conditions, the equipment replacement scheme of reduction project investment expense＜referring to Figure of description 5---the cheap facility synoptic diagram that substitutes, among the figure: 63-yellow phosphorus electric furnace, 64-U type is poor, 65-knockout tower body, 66-charging skirt, 67-low level discharge port, 68-high-order discharge port, 69-venting port, 70-sloping body soil property layer, 71-fire-resistant mixed earth, 72-thermal insulation layer, 73-liner (carbon brick or refractory brick), 74-groove lid, 75-circulation obstacle, 76-be bumped into inner liner portion 〉:

Be built in the project implementation enterprise on the higher topographical such as hillside for production equipments such as yellow phosphorus or pig iron smeltings, can utilize the hillside that is the α angle with the local horizon, excavate also and build one with refractory concrete and add a cover " U " type groove: be incubated insulation in the groove and serve as a contrast with carbon brick; Trench bottom is inlayed with carbon brick, electrode paste and is built random melt circulation obstacle, to force melt in the dirty process of eminence, bifurcated to take place repeatedly, converge, reach mutual stirring, mixing, satisfy liquid---uniform mixing and heat transfer requirement that solid matter interpenetrates, spreads; The groove lid is made the insulation insulation and some CO burners is installed.Simultaneously, at the foot of the hill, also the knockout tower that has charging skirt, global approximation " V " shape with anti-concrete placement one is connected with " U " shape groove.The knockout tower body has high and low position discharge port.Since the melt of discharging from " U " shape groove through and the body charging skirt of building that is connected as a single entity enter the knockout tower body from the bottom, so needn't add " funnel " formula feeding unit in the knockout tower;

Construction finishes, solid laid CO and combustion air supply line can the alternative techniques flow process in liquid---the batch mixing reactor (9) and the separating tank (10) of delaying time.And long " U " shape groove has strengthened liquid---solid-phase material stirs, mixes and carry out the time and intensity of chemical reaction, makes the cement clinker formation reaction more fully, fully, is that comparatively desirable, as not consume metallic substance cheapness substitutes facility.

In addition, at " technical problem 1 ", for strengthen the CO combustion gas to the heats of material, guarantee the cement clinker formation reaction reach flow of melt fully, the invention allows for and slag stored surge tank (1) is solid, liquid---the technical scheme that spray fusing heats is carried out in the charging utilization " combustion gas material spray fusing device " of batch mixing reactor (9) and time-delay separating tank (10) or cheap alternative facility.

Combustion gas material spray fusing device＜referring to Figure of description 6---combustion gas material spray fusing device structure principle chart is among the figure: 77-material inlet tube, 78-CO sleeve pipe, 79-casing air, 80-flame core (internal flame), 81-burning flame envelope, 82-material drop〉be actually the CO burner that a center is provided with, has increased a high temperature resistant material inlet tube.Melt or fritting material are entered by center material inlet tube, when spray fusing device nozzle place and CO and air mixed and the high velocity air lighted converge, smashed, break up and become the drop with certain diameter by air-flow.Meanwhile, more help to absorb the CO combustion heat because material specific surface area significantly increases: the droplet treatment material the inside and outside flame heat of spray fusing device and around under the collaborative heating of other burner, temperature raises rapidly and reaches the state of processing requirement;

The available steel pipe socket sealing of tube of the CO combustion parts of spray fusing device (being CO sleeve pipe, casing air) forms; But high temperature resistant, thermal insulation material manufacturing that the material inlet tube that is positioned at the center must adopt.It assembles mode with adopting screw thread being connected of CO combustion parts.The admission passage of CO and combustion air can not be exchanged during use, avoids the material inlet tube at high temperature to damage because of contacting with air;

The employing of combustion gas material spray fusing device will significantly improve the functioning efficiency of CO combustion gas to the material heating and melting, realizes the good operation of the present invention's process system;

Note also that: except that when adopting direct method calcination colored cement grog, needing to adjust the cement clinker of spray fusing device CO combustion atmosphere, calcining object color component according to the production purpose, the burning of spray fusing device CO should keep reducing atmosphere as far as possible: this not only helps the raising of cement clinker strength quality, but also because of Fe in unnecessary CO and the melt ₂O ₃Thereby the whiteness quality that chemical reaction has improved white portland cement clinker to a certain extent takes place.Therefore, this is the melt mode of entrance of a spray fusing heating of achieving many things at one stroke.The project implementation can suitably strengthen supply gas pressure on this basis, further strengthens the spray fusing effect, creates good processing condition.

At last, the contriver thinks, implement above-mentioned technological project and make to reach best-of-breed technology and market effect, and project implementation enterprise should also be noted that following problem:

1, to the insulation of industrial slag and cement melt, anti-condensation, anti-blocking, guaranteeing their flowability, is the matter of utmost importance that the project implementation faces.For this reason, must be simultaneously in the measure of the charging spray fusing heating of conversion unit that adopts " combustion gas material spray fusing device " as mentioned above or alternative facility, also to pay special attention to strengthen to key facility in the process unit or cheaply substitute the insulation measure that is provided with, guarantee CO combustion heat power, the preheating work before carrying out device and feeding intake, suitably increase mineralizer and (should use and contain BaCO ₃Or BaSiO ₄Compound mineralizer) add-on with reduce melt viscosity, and make great efforts to keep the burning clinker of cement operation continuously and uninterrupted running.The project implementation with good conditionsi enterprise also can take the mode of heated by electrodes, and is perfectly safe to protect.

2, should strictly control material qualities such as phosphorus production proportion scale and ore, nut coke, will note Fe in the raw materials such as ore, nut coke especially ₂O ₃The control of content.Fe ₂O ₃A large amount of existence, not only influence the normal operation of yellow phosphorus electric furnace, and the integral body that will cause rich iron melt spray bleaching operation to handle increasing the weight of of burden and white portland cement clinker whiteness quality descends.At this situation, enterprise with good conditionsi can carry out pre-treatment to the various raw materials of phosphorus production; Because the Fe in the phosphorus production raw material ₂O ₃Generated ferrophosphorus (Fe by C reduction back with phosphorus reaction ₂P).The removing ferrophosphorus work of slag is very important when therefore, carrying out the yellow phosphorus deslagging; Simultaneously, the nut coke that is mingled with in the slag also to carefully be removed;

3, CaO (lime), Al ₂O ₃Selecting for use of (alum scholar) and mineralizer, slow doubtful agent, various tinting pigment, cement additive etc. will be pursued high purity, high quality as far as possible, this is very important for producing high-quality, high-grade white and colored portland cement, avoids causing because of new quality problems of adding composition the influence of and quality inferior to the product retaining;

4, poor for raw materials for production such as yellow phosphorus or pig iron smelting, ore quality shakiness, working condition, produce the project implementation enterprise of higher white of quality requirements and colored portland cement again, can in cement melt micronize operating unit, also adopt the method for spray bleaching: install the formula sucker of emanating additional on the high pressure draft path of the cement melt that is being used for atomizing, suck the chemical bleaching medium, the poor iron cement melt relatively poor to whiteness carries out spray bleaching; Simultaneously, on pneumatic atomizer (12), also install loudspeaker expansion additional and put shape reinforcement cover, to improve bleaching effect.But must pay special attention to: under the situation that does not have the basic environment and the person, device security safeguards, must not use the CO gaseous reducing agent as the bleaching medium;

5,, can save rich iron melt settlement separate and spray bleaching, the sorting of grog whiteness and the operations such as warehousing, tinting pigment preparation of classifying for only requiring the enterprise that produces ordinary Portland cement.But these production practical situation that will make the process unit forfeiture adapt to industry such as yellow phosphorus and pig iron smelting fluctuate, satisfy the flexible production ability of cement changes in market demand.To this, project implementation enterprise should carry out sufficient market forecast and gain and loss evaluation;

6, process of flexible production method flow of the present invention, be under the high requirement of production quality product matter white and colored portland cement, taken into full account many secondary face factors such as the used ore of manufacturing enterprise, material quality and production technique fluctuation thereof such as different yellow phosphorus of each working condition and pig iron smelting, and made every effort to initiatively adapt to., controlling of production process higher for the raw materials for production quality is stable, Fe in its slag composition ₂O ₃Content is less and can keep stable, gained white portland cement clinker can guarantee to have whiteness quality, the working condition project implementation preferably enterprise higher or that market is satisfied, when implementing the present technique project, to cement clinker carry out the whiteness sorting and the classification warehousing also just there is no need, project implementation enterprise can be weighed according to s own situation, reduces the project investment expense as much as possible.

The contriver be sure of, present technique project implementation and popularization, will realize that numerous product slag industry such as yellow phosphorus and pig iron smelting combine, change the whole looks that the industry energy consumption is huge, seriously polluted, the industrial residue added value is low such as yellow phosphorus and pig iron smelting more closely with cement production industry, realization tradition product slag is industrial and the doulbe-sides' victory of cement production industry, and produce good economic benefit, ecological benefits and social benefit.

Claims (10)

1, a kind ofly produces cement with the yellow phosphorus high-temperature slag particularly white and colored portland cement, realization phosphorus production waste residue, used heat all utilize, possess the processing method of flexible production ability, it is characterized in that: before not changing former batching ratio of phosphorus production and processing condition, the former order of assurance phosphorus production and quality product, put the Inherent advantage that performance phosphorus production and slag oxide compound thereof are formed, by in slag, adding CaO, Al ₂O ₃Or other composition correction material and the mineralizer and the additional CO combustion heat; Gu at liquid---uniform mixing in batch mixing reactor (9) and time-delay separating tank (10) or the cheap alternative facility; heating and melting and successive reaction generate the fusion grog of white portland cement or other type cement; again through the air-flow micronize; the sorting of grog whiteness; the tinting pigment preparation; combined grinding; finished product warehouse-in and rich iron melt is settlement separate and flexible production operation such as spray bleaching; produce all kinds; particularly added value is higher; market outlook are good; have the white and the colored portland cement finished product that beautify and adorn function; what reach the phosphorus production energy and resource utilizes purpose jointly, also is specially adapted to pig iron smelting simultaneously or other produces the energy of slag industry and the comprehensive utilization of resource.

2, according to claim 1 described method, it is characterized in that: for generating the cement clinker of higher-strength quality, the first liquid of using---batch mixing reactor (9) carries out the uniform mixing and the initial reaction of raw material, mineralizer powder and slags such as composition correction Gu invention has been taked, enter again and be provided with " funnel " formula blanking device fully to react further in the time-delay separating tank (10) that strengthens the settlement separate effect of rich iron melt, guaranteed liquid---the uniform mixing and the cement clinker formation reaction time of solid-phase material,, reaction created condition for generating high-quality grog.

3, according to claim 1 and 2 described methods, it is characterized in that: as realizing the composition correction material, mineralizer and high-temperature slag uniform mixing also carry out the key equipment of the technological process of initial reaction, invention has been taked by support plinth, metal shell, thermal insulating warm-keeping layer, being provided with repeatedly level crossing and isolating two groups of melt dividing and the last reactor of discharging to play liquid---solid-phase material stirs and makes the batch mixing plate of uniform mixing effect, adiabatic cover plate and a plurality of CO fuel devices that are mounted thereon, advance, Gu liquid---the general structure design of batch mixing reactor (9) that parts such as discharge port and outlet port are formed has satisfied arts demand.

4, method according to claim 1, it is characterized in that: invent to improving and stable white Portland clinker whiteness quality, processing to the rich iron melt that influences grog whiteness quality is to form by settlement separate and two steps of spray bleaching, and is achieved by time-delay separating tank (10) and spray bleaching tower (27) two (cover) equipment configurations and the process system for nucleus equipment respectively.

5, according to claim 1 and 4 described methods, it is characterized in that: time-delay separating tank (10) removes possesses CO combustion gas heating, prolong the cement clinker formation reaction time, guarantee outside the process acts of clinker strength quality, also bear containing the irony composition higher, influence the settlement separate task of the rich iron melt of white portland cement whiteness quality: for strengthening its settlement separate effect to rich iron melt, the measure of " low level charging " has been adopted in invention especially, promptly adopt " funnel " type blanking device, put before heating and melting spatial CO combustion gas heating of separating tank top and the molten materials effect guaranteeing, make melt flow to separating tank (10) time-delay separated space bottom, and then strengthened settlement separate effect through " funnel " straight tube, effectively reduced spray bleaching operation treatment capacity.

6, according to claim 1 and 4 described methods, it is characterized in that: the bleaching to the rich iron melt that influences white portland cement clinker whiteness quality is with Fe ₂O ₃And the chemical reaction between the CO (or NaCl) is a ultimate principle, with spray bleaching tower (27) is nucleus equipment, with air-stream spraying, the contact reacts area that improves bleaching medium and cement melt is a reinforcing process, by by pneumatic atomizer (28), the formula of emanating sucker (29), cooling-water pump (30), tubular heat exchange (31), strengthen cover (32), control valve (33), (34), cleaning apparatus (35), the rich iron melt spray bleaching of a whole set of of releasing flare that equipment such as (36) and parts form system finishes, be to improve white portland cement product retaining in the flexible technology method flow, realize the key subsystem of project implementation maximizing the benefits, have crucial product retaining and reach the quality assurance meaning;

7, method according to claim 1; it is characterized in that: for electric power and the devices consume that reduces the grog powder-grinding process; and on technology, guarantee to white portland cement clinker whiteness grade sorting, make a complete set of process unit possess the flexible production ability, invention utilizes high pressure draft to pass through pneumatic atomizer (12) especially and has realized melting the spray particlesization of boiled water mud melt.

8, processing method according to claim 1, it is characterized in that: invention is by the continuous production that being provided with of slag storage surge tank (1) realized cement clinker, the practical situation that adapted to yellow phosphorus deslagging at intermittence, and the setting by standby former (material) feed bin (5), (20) and grog whiteness sorting mechanism (15) and corresponding classification to store work in-process storehouse technologies such as (16) adaptive, make a whole set of technology and device possess the flexible production ability, improved a whole set of processing method flow process and device adaptability greatly the phosphorus production practical situation and the cement market requirement.

9, method according to claim 1, it is characterized in that: be built in situation on higher topographical such as the hillside at production equipments such as yellow phosphorus that has or pig iron smeltings, the present invention proposes to build and be built-in with random melt circulation obstacle to play stirring along the hillside, mix, infiltration also makes liquid---solid-phase material uniform mixing, " ∪ " type of the adding a cover groove of frit reaction effect reaches and at the foot of the hill is connected with groove by the charging skirt, play the settlement separate effect of rich iron melt, approximate " V " Gu the cheap facilities such as knockout tower of shape with replacement liquid---batch mixing reactor (9), suiting measures to local conditions of time-delay separating tank (10), save the scheme of project construction investment, for the low cost construction of project provides a kind of selection.

10, method according to claim 1, its feature also is: for increasing the heats of CO combustion gas to material, what guarantee the cement clinker formation reaction reaches flow of melt fully, the present invention has also proposed especially to utilize and has been actually " the combustion gas material spray fusing device " that a center has increased the CO burner of a high temperature resistant material inlet tube, slag is stored surge tank (1), Gu the technical scheme of CO combustion gas spray fusing heating is taked in liquid---batch mixing reactor (9) and time-delay separating tank (10) or the cheap charging that substitutes facility, has improved the heating efficiency to material, satisfied arts demand.

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