CN1024810C - Detoxication and comprehensive utilization of waste residue and gangue containing chromium titanium nickel and vanadium - Google Patents

Abstract

The present invention belongs to the treatment of solid castoff, which is mainly used for detoxicating and comprehensively using waste fertilizer catalysts, electroplating sludge stainless steel swarf dust containing chromium and coal gangues in the processes of producing fertilizer, methanol, sulphuric acid, petroleum products and stainless steel, electroplating, etc. The castoff can be sintered and agglomerated, and the sintered blocks, waste fertilizer catalyst granules, the coal gangues (potassium feldspar), etc. are put in a blast furnace system and are smelted to obtain foundry iron (potasium fertilizer) which comprises chromium, nickel, titanium, manganese, silicon and vanadium and granulated blast furnace slag. The present invention achieves the purpose that chromium pollution and vanadium pollution are radically solved, and valuable elements, such as the chromium, the nickel, the titanium, the manganese, the silicon, the vanadium, iron, etc., are recovered in one step; the present invention has obvious social and economic benefit.

Description

Detoxication and comprehensive utilization of waste residue and gangue containing chromium titanium nickel and vanadium

The invention belongs to treatment of solid waste.Be mainly used in enterprises such as chemical industry, metallurgy, Coal Chemical Industry, petrochemical complex, plating, in producing processes such as chemical fertilizer, methyl alcohol, sulfuric acid, petroleum product, stainless steel and hydrogenating desulfurization, methanation, plating, containing 1-3% sexavalent chrome and multi-component useless chemical fertilizer catalyst such as nickel, vanadium, contain the improvement of chromium, nickel electrodeposited chromium mud, depleted coal gangue, stainless steel grinding dust dirt its discharge, reach thorough detoxifcation, non-secondary pollution, resource utilization and comprehensive utilization.

Useless chemical fertilizer catalyst: 1988, useless abroad chemical fertilizer catalyst is annual discharged about 6.78 ten thousand tons, was located at special recovery spent catalyst factory mostly and was reclaimed and be used (" the chemical fertilizer catalyst recovery technology of giving up " " middle nitrogenous fertilizer " the 1st phase in 1989).

The seventies, K (but is contained with the useless chemical fertilizer catalyst of similar this kind in chemical plant, Japanese heavy chemical industry company nine continent ₂CO ₃Except) make ferrochrome through electrosmelting reduction, contain Cr in the slag ₂O ₃＜1%, sell (translation: " the resource utilization present situation and the prediction of used catalyst ", author: Zhoushan three heros) as pavior.Tokyo ceramic industry company once was contained in this type of spent catalyst in the plumbago crucible, in high-frequency furnace, smelt, obtain containing the ferrochrome of Cr5.88%, the rate of recovery reaches 98.6%, as smelting the steel alloy usefulness (Japan's patent gazette, clear 52-156712) that heat-resisting Gao Ge (the containing Cr12-15%) trade mark is SCH-1.Roasting behind the low-melting fusing assistant of interpolation after the mutual clear mining company of Japan pulverizes spent catalyst is as ceramic glaze.

U.S. KatalCo company adopts dilute sulphuric acid to dissolve the sulfate liquor that this type of spent catalyst obtains chromium and iron, adds Ca(NO again ₃) ₂Make it be converted into Fe(NO ₃) ₂And Cr(NO ₃) ₂Mixed solution can be used for preparing raw catalyst.U.S. mineral bureau albany research center reclaims chromium with the fused-extracting method in useless transformation catalyst, with Na ₂CrO ₄Form is as the finished product.

The used HNO of Soviet Union's Kiev industrial research ₃Again use ammonia precipitation process with the preparation raw catalyst after dissolving this type of spent catalyst, and commerical test was carried out in the Huangshui River thatch gram chemical joint venture catalyzer workshop of having paused in north.

Chemical fertilizer industry institute of the domestication Ministry of worker once with spent catalyst like the group categories, used H after crushed ₂SO ₄, replenish chromic anhydride (CrO ₃) to adjust component, this kind raw catalyst is made in step precipitation, filtration, drying, roasting, moulding etc. again routinely again then.Tianjin Chemical Research Institute of Ministry of Chemical Industry was also once studied in the scrap iron chromium-based catalysts of associating with Na ₂CrO ₄Form reclaims the technology of chromium.More domestic catalyst manufacturers also all were engaged in the recovery of useless chemical fertilizer catalyst as: colleges and universities such as catalyzer subsidiary factory of Shichuan Chemical Factory, Chemical Fertilizer Plant, Jilin Chemical Industry Co., Gongzhuling catalyst plant, Nan Hua company catalyst plant and Hebei Polytechnical College, Northwest University, or trial-production dyestuff (chromium tinting material) etc.But, accomplish thorough detoxifcation, non-secondary pollution resource utilization and comprehensive utilization person again, there is no both at home and abroad.

Electrodeposited chromium mud: plating is that a kind of important technology that adds is planted in the modern industry.The high concentration chrome wastewater that electrodeposited chromium produces has toxicity and carcinogenesis to biology.Contain Cr in the electroplating industry ^{+ 6}Chemical method is extensively adopted in the improvement of sewage at home and abroad, and electroplating chromium-containing sludge is that it uses chemical method improvement to contain Cr ^{+ 6}The sediment that produces during sewage-contain Cr ^{+ 6}Mud belongs to a worldwide improvement pollutent difficult problem.

Contain Cr in the mud of electrodeposited chromium factory ^{+ 6}With Cr ₂O ₃Meter is up to 5-20%, and most producers sneak into Xia Shui with it and drain, and the factory that has stores up, and indivedual factories are are just researching and developing application.As Chinese invention patent " electroplating chemical method waste residue system chaba powder " (on March 1st, 1987 is open, and publication number is: CN861077A), and Chinese patent " chemical method is administered and is contained Cr ^{+ 6}The utilization of electroplating wastewater and sediment " (number of accepting is: 88106261.8).

Administer both at home and abroad to electroplate and contain Cr ^{+ 6}There is following shortcoming in the method for mud: the detoxifcation that (1) has is not thorough, and Cr is still arranged ^{+ 6}Pollute, (2) can not reclaim valuable elements such as Cr, Ni in the electrodeposited chromium mud; (3) consumption is few, energy consumption height, deficiency in economic performance.

Stainless steel grinding dust dirt: China's stainless steel production line all has the Cr of containing, Ni, Ti, Fe, dust, bits grain every year, and cutting slag etc. is thrown aside.Roll as (1) that sack dust contains Cr3-5%, Ni4-0.6%, TFe50-70% in factory's shot-blasting machine sack cleaner; (2) sack dust contains Cr5-7%, Ni2-5%, TFe30-40% in the argon oxygen stove sack cleaner; (3) sack dust contains Cr5-8% in rough rolling mill's sack cleaner, Ni1-3%, and TFe35-45% etc. effect a radical cure for a long time, and the hole is thrown aside, filled out to majority, causes the wasting of resources, contaminate environment.

Coal gangue: coal gangue is present in the stratum in the cambrian period in the Pz, is that a kind of carbon content is lower, but contains the mineral of multiple valuable element and other useful matter.Its content in coal accounts for 15-30%, as: China has 100,000,000 tons to take out of from coal production every year approximately, the whole nation totally store up coal gangue reach the number pick up hundred million tons more than, it accounts for a large amount of arable lands; The spontaneous combustion of cash mountain is easily caught fire, and generation contains SO ₂, H ₂Toxic gas such as S, CO, the atmosphere around polluting is suddenly waited to administer, with its development and use, turn harm into good, turn waste into wealth.The coal gangue composition is roughly (because of different from different places):

C10-25% SiO ₂30-50% Al ₂O ₃10-46% F ₂O ₃1-10% CaO1-4% MgO1-3% (TiO ₂Xiyang, 1-2% Shanxi) (V1-2% changde, hunan) N0.3-2%H ₂O1-5%

Thermal value 4184-10460 thousand Jiao/kilogram

The main application of coal gangue: 1, Xuzhou Chang Mount cement mill year is with 50,000 tons of coal gangue power generations, with the recrement after the burning as producing cement and novel wall material.Not only reduce environmental pollution but also saved 9 years 14 days nineteen ninety of farmland stacking (" mining machinery Shi Chang Bao "), the 9th phase), 2, Jiangsu brass hill chemical company and Jiangsu coal gangue comprehensive utilizating research institute are developed into the novel packing material of SAC-1, replace carbon black to be used for sebific duct production as strengthening agent, adopt the operational path of grinding of roasting-grindings-again, used the SiO in the coal gangue ₂, Al ₂O ₃And C(" Shanxi chemical industry ") on December 30th, 1989, the 24th phase).3, with coal gangue production crystallization aluminum chloride (" Shanxi chemical industry ") the 4th phase of nineteen ninety); Produce aluminium chlorohydroxide novel process (" Shanxi chemical industry ") the 3rd phase of nineteen ninety).4, the evergreen facility in Hongdong County, Shanxi factory extracts Al from coal gangue ₂(SO ₄) ₃, polymerization AlCl ₃With active A l ₂O ₃(" Shanxi science and technology newspaper ") etc.

There is following deficiency in the contrast of above-mentioned improvement coal gangue method and this patent: (1) generating, used wherein C and silico-aluminate wherein, as CaO, MgO, SiO ₂, Al ₂O ₃Deng the materials for wall of system cement, but the precious metals element in the coal gangue is failed to extract utilization.(2) operational path that has is long, the energy consumption height, and economic benefit is low; What have has only used C and SiO wherein ₂, Al ₂O ₃, fail to make full use of other Chemical Composition of coal gangue.(3) system crystalline A lCl ₃Deng the aluminium product salt, all thoroughly do not solve the problem of complex utilization of secondary pollution and recrement.Patent of the present invention can disposablely make full use of the chemical ingredients that mainly contains usefulness in the coal gangue, as: C, SiO ₂, Al ₂O ₃, MgO, CaO etc., also will be wherein contained metal oxide be reduced into element, obtain to contain chromium, nickel, titanium, ferro-vanadium.

In the recent period, detoxifcation of Chinese invention patent application number 88104766.X chromium slag high-temperature fusion and comprehensive utilization method are to administer chromium salt factory and the poisonous chromium slag of ferroalloy works' discharge, and detoxifcation is thorough, non-secondary pollution.But this method and the present invention relatively have following shortcoming:

(1), only can this a kind of deleterious chromium slag of disposable radical cure;

(2), the gained chromium cast iron contained, main component contains Cr 〉=12%;

(3), its granulated bf slag quality coefficient K is 1.4-1.7＞1.2, active slag in the genus;

(4), energy consumption height, economic benefit are low.

The objective of the invention is to be to overcome the individual curing and the secondary pollution problem of above-mentioned four kinds of wastes, easily handle simultaneously four kinds of wastes are disposable, comprehensive utilization is turned waste into wealth, and non-secondary pollution is obtained obvious social and economic benefit.

(contain K with the useless hts catalyst of certain fertilizer plant ₂CO ₃, Na ₂CO ₃Do not limit) and Electroplate Factory's chromium mud, certain steel mill's stainless steel grinding dust dirt and local coal gangue etc. be former, auxiliary material; on 19 square metres of blast furnace system production equipments of Xiyang County, Shanxi Province improvement chromium slag factory, carried out type approval test; through pyrotic smelting detoxifcation and comprehensive utilization; produce and contain Cr, Ni, Ti, Mn, Si, the V pig iron; high active granulated blast furnace slag system cement or building material product reach and turn harm into good, and turn waste into wealth; decontamination, the purpose of bringing benefit to the mankind.Simultaneously, obtain tangible environmental benefit, social benefit and favorable economic benefit.

In order to achieve the above object, the present invention has taked following main technical schemes:

To give up chemical fertilizer catalyst through screening, and the particle of about φ 9 * 8 sizes is for preparing burden, directly add blast furnace on the sieve; The minus sieve material need send the sintering field, with electrodeposited chromium mud, the stainless steel grinding dust dirt-above-mentioned powders such as chromium, nickel, titanium, vanadium that contain, arrange in pairs or groups, make up by on-site actual situations, both one of or both sums; Or combined methods such as thrin or three's sum are prepared burden, look and collect the above quality and quantity that contains solid waste such as chromium, nickel, titanium, vanadium, and flexibly batching, tissue produce-with red clay, coke powder by batching requirement mixing after, sinter the sintering lump ore into; Auxiliary materials such as this sintering lump ore and coal gangue, flux are by blast-furnace smelting, carbon heat reducing, and high-temperature fusion, layering separate, and can get fine by iron notch and contain Cr, Ni, Ti, Mn, Si, the V pig iron; Slag notch gets high active granulated blast furnace slag, can make cement high-quality blended material or building material made, as small-sized hollow building block etc.

By sintering process, most Cr in useless chemical fertilizer catalyst powder, electrodeposited chromium mud, the stainless steel grinding dust dirt ^{+ 6}Deng, with Cr ^{+ 6}Be changed to example explanation, C, Cr, Ni, Fe, FeO, CO in its mixed material reduce, generation Cr ₂O ₃, be the trivalent chromium form and have former contained Cr ^{+ 6}Have and be reduced detoxifcation more than 95%; Remaining through blast-furnace smelting, carbon heat reducing, a large amount of trivalent chromiums that a small amount of remaining sexavalent chrome in sintering lump ore Central Plains and new reduction generate all are reduced into chromium metal and enter in the iron liquid in blast furnace, surplusly in like manner analogize, generation contains Cr, Ni, Ti, Mn, Si, the V pig iron, so detoxifcation thoroughly.Cr ^{+ 6}All reach the emission standard of national environmental protection regulation Deng content in blast furnace production system water, gas, slag, thereby effected a radical cure Cr effectively ^{+ 6}Deng pollution to environment.

Simultaneously, auxiliary materials such as sintering lump ore and coal gangue are through blast-furnace smelting, have disposablely reclaimed valuable elements such as Cr wherein, Ni, Ti, Fe, Mn, Si, V effectively, and have made full use of the C in the coal gangue, have reduced coke ratio.The granulated bf slag of coproduction, contained trace sexavalent chrome is confined in vitreous structure in the slag, exists with the aluminosilicate mineral (spinel ore deposit phase) that contains chromium, belongs to the insoluble material, so thorough this conclusion of this technology detoxifcation is undoubtedly.The quality coefficient of granulated bf slag 〉=1.65 are to produce the high-quality blended material of cement or the desirable feedstock of producing building material mades such as small-sized hollow building block materials for wall.

Under the major technique characteristic series of the present invention:

1, most raw materials are to take from deleterious solid waste in the agglomerate batching, as: Fe-Cr series, vanadium series catalyst powder in the useless chemical fertilizer catalyst series, electrodeposited chromium mud, stainless steel grinding dust dirt; Useless coke powder and pulverized anthracite after collection powdered carbon or pulverized anthracite can sieve with metallurgical coke or hard coal; Be equipped with red clay again and make binding agent, and make full use of and wherein contain SiO ₂, Al ₂O ₃, Fe ₂O ₃Deng compound.

2, consider that agglomerate is former, auxilliary, on the proportioning of fuel, a reductibility and a self-fluxing nature guarantee sintering the time guarantees fixed carbon (general sintered ore for iron-smelting is prepared burden, and its fixed carbon is 3-4%) more than 4-7%; The 2nd, quaternary basicity (CaO+MgO)/(SiO ₂+ Al ₂O ₃) should be controlled at 0.8-1.25, dual alkalinity (CaO/SiO ₂) should be controlled at 0.5-0.9.

3, original and different in sintering process and the batching, take to be equipped with auxiliary materials such as red clay, make into low temperature self-fluxing nature reduction sintering process, the one, guarantee fully reduction Cr ^{+ 6}; Two will improve the sufficient intensity of agglomerate.FeO, the NiO, the CO that produce in self-fluxing nature reduction sintering process can further reduce Cr ^{+ 6}Deng, thereby eliminated chromium, pollution of vanadium basically.

4, blast-furnace smelting system has captured seven technical barriers, is specified in the back:

(1) potassium, the sodium behavior in blast furnace: it is generally acknowledged that potassium, sodium takes in greater than expenditure in blast furnace, redundance at the blast furnace internal recycle, accumulate to a certain degree, make refractory brick surface quarrelization, easily in blast furnace top dross, havoc blast furnace ordinary production.So regulation is gone into alkalimetal oxide (K in the furnace charge ₂O+Na ₂O) must not surpass 0.5%; Going into furnace charge abroad is limited in the pig iron per ton and is no more than the 2-4 kilogram.In addition, also easily corrode lining of fire brick at bottom house.

And this technology is gone into that stove is former, auxilliary, alkali metal oxide content has surpassed 4 kilograms of/ton iron and (just contains K because of what have in the chemical fertilizer catalyst that gives up in the fuel ₂CO ₃, Na ₂CO ₃), even in blast-furnace burden, add the part potassium felspar sand, contain K in the granulated bf slag ₂O0.3-1.0%, Na ₂O0.2-0.5% also can not form accretion.Production practice prove: potassium, sodium are with KHCO in the furnace charge ₃, K ₂CO ₃, NaHCO ₃, Na ₂CO ₃Account for more than 80% from the furnace roof discharge with furnace gas etc. form.And stove bottom refractory brick liner is etched to a certain degree, still can keep ordinary production by the water-cooled thickness of the slag crust.For this reason, the present invention has pulled through blast furnace this " forbidden zone " (" potassium felspar sand system salt of wormwood coproduction white fused cement " " inorganic chemicals industry " 1988 the 1st phases).

(2) when blast-furnace burden, can disposable four or more (above-mentioned sintering lump ore and auxiliary material coal gangue etc.) component complexity, source of pollution be disperseed, pollute the wide Cr that contains ^{+ 6}(or vanadium) deleterious solid waste (promptly useless chemical fertilizer catalyst, electrodeposited chromium mud, stainless steel grinding dust dirt and coal gangue etc.) puts together, and effects a radical cure decontamination in this production line.

(3) can disposable useful component main in the coal gangue, i.e. C, the SiO of utilizing ₂, Al ₂O ₃, Fe ₂O ₃, (or Fe ₃O ₄), TiO ₂Deng, the comprehensive utilization degree height.

(4) in blast furnace ironmaking process, disposable Cr, Ni, Ti, Fe, Mn, Si, the valuable element of V of reclaiming simultaneously of energy, generation contains chromium, nickel, titanium, manganese, silicon, ferro-vanadium.

(5) contain TiO in the auxiliary materials such as red clay, coal gangue and bauxitic clay in the batching ₂, when furnace charge enters the high temperature reduction district, titanium is reduced, generates compounds such as TiC, TiN and TiCN, is viscous foam shape slag, causes that slag iron is difficult to be divided.This technology is by taking batching, stove up-down adjustment, water-quenched blast-furnace slag, quenching, measures such as big yield flushing cinder, thereby head it off.

(6) tap cinder is that the symmetric double slag notch is slagged tap, with pressure shrend, quenching, big yield flushing cinder, granulated bf slag quality coefficient

K＝[（CaO+MgO+Al ₂O ₃）/（SiO ₂+MgO+TiO ₂）]≥1.65，

The regulation that surpasses K＞1.2 among the standard GB 263-78 is a high-quality active mixed material of producing cement.

(7) MgO content must not be above 5% in the regulation grog in silicate cement is produced; (MgO of dead roasting state) enters cement and cement products when periclasite, can cause the inhomogeneous variation of cement stone volume, because the aquation of the main clinker mineral of the aquation of magnesite will be slowly many, it occurs in hardened sand-cement slurry or the concrete, and be accompanied by huge volume change, because periclasite (MgO) aquation generates Mg(OH) ₂The time, solid volume increases to 2.48 times, gently then reduces buildings intensity, causes construction cracking and collapse when serious, and Here it is, and MgO causes the reason that soundness of cement is bad.

And above-mentioned with MgO content in useless chemical fertilizer catalyst powder and the sintering lump ores through sintering into such as electrodeposited chromium mud, stainless steel grinding dust dirt at 6-18%; through blast-furnace smelting; contain MgO up to 6-18% in the granulated bf slag that generates, but it is present in the glassy phase, with spinel MgO-Al ₂O ₃Form occurs, it is a kind of state finely divided, that combine with other compound, it as the Additive in the operating mine slag portland cement (in the time of can mixing the 30-40% weight percentage), can be made cement have normally to condense, all even gain in strength of volume change.Through petrofacies and X-diffraction analysis result, do not have free MgO(periclasite in this kind granulated bf slag), soundness of cement there is not influence.At this, MgO also can reduce the viscosity and the fusing point of blast-furnace slag, makes slag be easy to vitrifying.

Press the phasor principle; strict blast furnace zooming batching; distinguish the refining slag and be main with smelt iron different; grasp its key; should guarantee to bring into alkalimetal oxide discharges out of the furnace from furnace gas and slag effectively in large quantities; guarantee the activity and the quality coefficient K of granulated bf slag again, be system cement and the good condition of building material made creation.

Simultaneously, hot blast temperature is grasped in operation meticulously, comprehensively judges the working of a furnace, adopts suitably big air quantity, and the air-supply coefficient is generally 2-5 at 5-7(); Control furnace temperature and slag composition and basicity of slag reach more than 80% the rate of recovery of Cr, and the rate of recovery of Ni reaches about 85%, and the Ti rate of recovery about 70%, the Fe rate of recovery are more than 90%, and the V rate of recovery is then more than 60%.

Fig. 3 is seen in technical process of the present invention.

Production process of the present invention is summarized as follows:

One, sintering

1. sintered material

1, mainly former, auxilliary, the fuel of agglomerate are: useless chemical fertilizer catalyst powder, and its granularity is less than 5 millimeters (as powder such as useless hts catalyst, spent vanadium catalyst, useless conversion catalysts); Electrodeposited chromium mud, granularity is less than 1 millimeter; Stainless steel grinding dust dirt, granularity is less than 5 millimeters; Red clay or kaolin, bauxitic clay, granularity is less than 4 millimeters; Coke powder or pulverized anthracite, granularity is less than 5 millimeters.

The proportioning of each material (weight %) row are down in the batching:

(1) useless chemical fertilizer catalyst powder: electrodeposited chromium mud: stainless steel grinding dust dirt: pulverized anthracite or coke powder: red clay=1-30%: 1-15%: 20-60%: 10-30%: 10-25%

(2) useless chemical fertilizer catalyst powder and/or stainless steel grinding dust dirt: electrodeposited chromium mud: coke powder or pulverized anthracite: red clay=20-65%: 1-20%: 10-30%: 10-30%

(3) useless chemical fertilizer catalyst powder and/or electrodeposited chromium mud: stainless steel grinding dust dirt: pulverized anthracite or coke powder: red clay=20-40%: 6-30%: 10-30%: 10-25%

The composition of each material (weight %) is shown in table 1, table 2, table 3, table 4 in the batching.

2, batch mixing

Prepare by above-mentioned former, auxilliary, fuel ratio metering, drop in the powerful reverse-flow muller of QH14 type, and add the water of 10-15% simultaneously, carry out thorough mixing, the compound of mixing send sintering field sintering for agglumeration.

3, sintering

In technical process that the present invention proposes and the raw materials for sintering batching, useless chemical fertilizer catalyst powder, electrodeposited chromium mud and stainless steel grinding dust dirt bulk cargo can not directly add blast-furnace smelting, need can go into stove and smelt after sinter molding is made the sintering lump ore.

With the above-mentioned material to be sintered for preparing mixing, all can carry out sintering by sophisticated " method is blown on the level land " and box exhausting mechanize sintering process.Be specially: furnace bottom arranges (shop stove), igniting, material loading, accent fire, banking, repair stove operates meticulously with orders such as sky blow.When the sintered material temperature rose to 850-1400 ℃ of high temperature, coke burning generated CO, the CO Na in chemical fertilizer catalyst, the electrodeposited chromium mud that will give up ₂CrO ₄, CaCrO ₄, Cr(OH) ₂, Cr(OH) ₃And CrO ₃Become Cr Deng the chromium overwhelming majority reduction that contains in the chromium cpd ₂O ₃, the back is listed in its principal reaction:

In sintering process, owing to contain C in the above-mentioned blended stock, metal Ni, NiO, existence such as metal Fe, FeO make Cr ₂O ₃, CrO ₂Easily be reduced, produce CO, NiO and FeO simultaneously, they are CrO equally ₂And CrO ₃Reductive agent.CrO ₂, CrO ₃Generate Cr with C, CO, Ni, NiO, Fe and FeO reaction ₂O ₃Free energy △ F ⁰Under the value.Therefore, in sintering process, CrO ₂And CrO ₃Be reduced the most at last and generate stable Cr ₂O ₃, can not generate CrO and Cr ₃O ₄Or Metal Cr; Do not have more CrO ₂And CrO ₃Exist, and can only be micro-.

Facts have proved that it is high more to contain C, Fe, Ni amount in the above-mentioned compound that is sintered, it is thorough more that then sexavalent chrome is reduced into trivalent chromium.The sexavalent chrome overwhelming majority is reduced into trivalent chromium behind sintering, and its reduction ratio reaches more than 95%, and hexavalent chromium amount reaches the emission standard value of national environmental protection regulation all less than 0.01% in the agglomerate, can supply blast-furnace smelting.

Behind C all burnt in the sintered material, temperature of charge descends gradually, the above-mentioned waste residue sintered materials such as chromium, nickel that contain begin crystallization and fixed by pasty state, separate out new mineral, form and to contain waste residue agglomerate such as chromium, nickel, every technical indicator of its composition and metallurgical physicals all meets the requirement that blast-furnace smelting contains Cr, Ni, Ti, Mn, Si, the V pig iron.

After above-mentioned agglomerate treats that it cools off fully, through broken, be sized to the 15-50 mm particle size, batching is gone into blast furnace.Above content is please referring to " small blast furnace ironmaking technology " (Xi-an Metallurgical Construction College ironmaking chamber, in October, 1979,47-51 page or leaf); " vanadium, chromium tailings system self-fluxed sinter-vanadium, chromium tailings fully utilize and remove chromic research (one) " (" iron alloy " 1987 the 3rd phases); " vanadium, chromium tailings agglomerate analog blast furnace are smelted pig iron containing vanadium-vanadium, the comprehensive utilization of chromium tailings and removed chromic research (two) " (" iron alloy "), 1987 the 4th phases); Chinese invention patent " chromium slag high-temperature fusion detoxifcation and comprehensive utilization " (patent of invention number No. 11104, application number: 88104766.X) and " the thing phase composite of chromium slag and to the influence of chromium residue detoxifying and comprehensive utilization " (" chemical industry environmental protection " 1984 the 4th the 1st phases of volume).

After table 5 is seen literary composition

Two. blast-furnace smelting

Contain with above-mentioned that waste residue agglomerates such as chromium, nickel, the about Φ of granularity 9 * 8 millimeters useless chemical fertilizer catalyst particles, lime or Wingdale, coal gangue, fluorite and coke (can the calorific value height, the anthracite block coal of the 1/4-1/2 of the standard compliant total coke of thermostability substitute) be broken respectively, screening is the 15-50 mm particle size, by quaternary basicity (CaO+MgO)/(SiO ₂+ Al ₂O ₃) be 0.85-1.25, dual alkalinity (CaO/SiO ₂) be controlled at 0.95-1.35 and prepare burden.

1, above-mentioned agglomerate: useless chemical fertilizer catalyst particle: coal gangue: coke (can the calorific value height, the anthracite block coal of the 1/4-1/2 of the standard compliant total coke of thermostability substitute): lime or Wingdale: fluorite=0-40%: 0-40%: 10-15%: 20-35%: 20-35%(is in lime, down with): 1-2%(weight).

2, above-mentioned agglomerate and/or useless chemical fertilizer catalyst particle: coal gangue: coke (the same, slightly): lime or Wingdale: fluorite=20-50%: 10-18%: 20-40%: 18-35%: 1-2.5%(weight).

By batching, go into furnace charge and criticize and be: above-mentioned agglomerate 150-280 kilogram; Useless chemical fertilizer catalyst particle 0-250 kilogram; Lime 100-260 kilogram; Coal gangue 40-140 kilogram; Fluorite 5-15 kilogram; Coke (ditto, slightly) 120-320 kilogram.Promoting truck 1 to furnace roof by windlass drops in the blast furnace 2.Smelting the above-mentioned processing condition of waste residue agglomerate such as chromium nickel etc. that make in blast furnace is:

(1) blast furnace blast amount 100-140 rice ³/ minute;

(2) cold wind pressure 320-560 mmhg;

(3) hot blast temperature 950-1100 ℃

(4) throat temperature is controlled at 200-300 ℃

(5) flushing cinder shrend water pressure 0.3-0.6MPa;

(6) the shrend water temp is less than 60 ℃;

(7) slag iron is than 1.5-6.0 Water Quenching Slag ton/contain pig iron tons such as chromium, nickel;

(8) system slag coke ratio 300-550 coke kilogram/Water Quenching Slag ton;

(9) coke load 2.0-3.8 goes into stove ore deposit ton/coke ton.

On the state of 1450-1480 ℃ of slag notch temperature, smelt (process flow sheet sees Figure of description for details).

Blast-furnace smelting is the summation of many physics and chemical process.Fuel ceaselessly moves upward by a large amount of high-temperature reductibility coal gas of hot blast burning generation before the air port, and constantly interacts with the furnace charge that descends.Furnace charge decline process at first is heated and effusion free-water, combination water etc. and a part of volatile substances; When waiting to reduce to 900 ℃ of left and right sides in shaft district, Wingdale decomposes, and generates active very strong CaO.Acid burden material occurs and basic stock contacts with each other, exchanged CaO, MgO and SiO mutually ₂, Al ₂O ₃Deng, begin solid state reaction from the surface, thereby make furnace charge softening gradually.When furnace charge is reduced to 400-1500 ℃, acidic oxide SiO in basic oxide CaO, MgO and the coal gangue ₂And Al ₂O ₃Reaction; The furnace charge fusion also generates 2CaO.SiO gradually ₂, MgO.Al ₂O ₃, 2CaO.Al ₂O ₃.SiO ₂, 2CaO.MgO.SiO ₂Deng mineral composition, promptly carry out the slag making reaction, form first slag.

Go into the metal oxide Cr that brings in the furnace charge ₂O ₃, NiO, TiO ₂, Fe ₂O ₃, FeO, MnO, Mn ₃O ₄, V ₂O ₅Deng, descend along furnace roof, the coal gas indirect reduction of being risen simultaneously enters the 1600-1800 ℃ of whole fusions of quilt in cupola well high-temperature zone, air port at last, metal oxide directly is reduced into element state by C in cupola well, and carry out slag and contain Cr, Ni, Ti, Mn, Si, the layering of V pig iron fused solution separates.Its principal reaction may for:

In smelting process, the CaO in the blast furnace 2, MgO, SiO ₂, Al ₂O ₃All dissolve and generate first slag until forming finishing slag Deng compound, slag tap by symmetric two slag notches (open close interruption slag tap by turns), through pressure water water granulation blast furnace slag.The shrend water pressure is that a large amount of cold water shrend quenchings of 0.3-0.6MPa are handled, and makes into the granulation particle of 0.3-7 millimeter size, is called granulated bf slag.Its concentrated flow of quenching is downstream gone into water quenching pool 6, pull, send the stockyard draining out through dragveyer 7, again by conveyor 9 through magnetic separator 8 select contain Cr, Ni, Ti, Mn, Si, V pig iron grain after, enter cylinder material feeder 10, the wet slag of water content 20-30% and binding agent, cement etc. are quantitatively added to enter in the powerful reverse-flow muller 11 of QH14 type mix.Compounds such as the granulated bf slag behind the mixing, cement are delivered to shaper 12,13 through conveyor, are pressed into small-sized hollow building block and large hollow building block 14 sales respectively.The small-sized hollow building block specification is: 390 * 190 * 190 millimeters; 1006 kilograms/meter of unit weights ³;

Ultimate compression strength 5-10Mpa; About water ratio 2%; Transformation ratio 0.93-0.95; 3.0396 watts/meter of thermal conductivitys. degree centigrade.

According to local circumstances, also granulated bf slag can be sold to the cement mill and make the cement Additive or make other building material mades.

In smelting process, in the blast furnace 2 above-mentioned contain the metal oxide that contains in waste residue agglomerates such as chromium, nickel, the useless chemical fertilizer catalyst particle etc. be reduced into contain Cr4-20%, contain Ni1-5%, contain 0.5-2%, contain Mn0.1-1.4%, contain Si1.5-6%, contain V0.1-1.2%(and this composition is arranged if add spent vanadium catalyst time side) pig iron, flow into pig-casting machine through blast furnace iron notch, trough, make into heavily about about the 12 kilograms ingot of piece.

Purified gas through dust-removal system is come out generally contains CO24-30%, CO ₂8-13% etc. enter pebble stove 4 and burn, and the tail gas after the burning is through chimney 5 emptyings.Fresh air is sent into pebble stove 4 heating by gas blower, and it is combustion-supporting to enter blast furnace 2 after being heated to 950-1100 ℃.

Fig. 1 containing chromium titanium nickel and vanadium waste residue and gangue detoxifcation comprehensive utilization process schema (Figure of description).

1, truck 2, blast furnace 3, sack cleaner 4, hotblast stove 5, chimney 6, water quenching pool 7, machine for fishing out 8, magnetic separator 9, conveyor 10, material feeder 11, the powerful reverse-flow muller 12 of QH14 type, small-sized hollow building block shaper 13, large hollow block machine 14, holllow building block finished product

Three waste discharge and environmental monitoring

(1) technology profile, main discharge and sampling optimization:

Accompanying drawing (Fig. 2) is seen in " three wastes " discharge and environmental monitoring in the containing chromium titanium nickel and vanadium waste residue and gangue detoxifcation comprehensive utilization technological process of production.

Because the characteristics of this technology are with by handling the deleterious above-mentioned waste residues such as chromium, nickel, titanium, vanadium, manganese, silicon that contain, produce industry chromium, nickel, titanium, manganese, vanadium, the silicon pig iron of containing in short supply, be one and turn harm into good, the novel process that turns waste into wealth, its remarkable in economical benefits.In order to investigate the environmental benefit of this technology, understand that the chromic content of objectionable impurities is vital in the pollutent of this art production process discharging.Know that from technical process this art production process discharges chromyl principal pollutant and is: the dust-laden blast furnace flue gas that (1) blast-furnace smelting produces; (2) blast furnace flue gas is through gravitational precipitator, sack cleaner and the aggegation of chimney internal cause and various dusts; The pulp water of quenching when (3) blast furnace ironmaking process is discharged waste residue; (4) Water Quenching Slag of blast furnace ironmaking process discharge.In view of the above, this monitoring sampling mainly to as if blast furnace emptying flue gas, various ash sample, waste residue sample and relevant water sample.Fig. 2 is seen in sample collecting point position.

(2) test purpose

The main purpose of this test is Cr in each discharge before and after relatively change the line of production (1) ^{+ 6}The changing conditions of content; (2) easily release Cr in each discharge after investigation is changed the line of production ^{+ 6}The possibility that has level and environment is polluted.

(3) content measurement:

1, gaseous state Cr in the emptying flue gas ^{+ 6}Content;

2, Cr in the emptying flue dust ^{+ 6}Content;

3, Water Quenching Slag water-solubility Cr ^{+ 6}Content;

4, blast furnace smoke evacuation gravitational dust, sack dust and chimney soot water-solubility Cr ^{+ 6}Content;

5, the Cr in the pulp water that quenches ^{+ 6}Content;

6, Cr in the recirculated water ^{+ 6}Content;

7, Cr in the supplementary feed ^{+ 6}Content.

(4) testing tool and method:

This test, various samples have adopted different samplings and analytical procedure respectively.The emptying flue dust adopts prediction flow velocity isokinetic sampling method, by the diphenyl carbazide spectrophotometry analysis in " air and waste gas analytical procedure "; The gaseous state chromium compounds adopts hot water glass plate absorption process to gather in the emptying flue gas, according to the diphenyl carbazide spectrophotometry analysis in " environmental monitoring and analysis method "; Ash, slag are by international GB5806-85 requirement sampling and sample preparation, and according to the diphenyl carbazide spectrophotometry analysis in " water and effluent monitoring analytical procedure ", the water sample analysis method is with ash, slag specimen.

Key instrument used during test has:

1, SYC-1 type smoke detecting instrument (the grand instrucment and meter plant in Shanghai);

2, S type Pitot tube;

3, tilting micromanometer

4, wetbulb thermometer;

5, chromel-constantan thermocouple;

6, the multi-functional vibrator of ZD-3 type;

7,721 type spectrophotometers.

(5) test operating mode and sampling frequency:

Monitoring is at the 19m to be changed the line of production of this factory before changing the line of production ³Carry out under the operating mode of the normal stably manufactured of iron-smelting blast furnace.Flue gas, flue dust are respectively taken a sample 3-4 time, respectively the head of ironmaking production cycle, in, the tail stage carries out.Ash, each sampling of slag per tour every day once connect and got two days, and mixing screening back is as the analytical test sample.Water sample minimum respectively getting once every day connects and adopted two days.

The back monitoring of changing the line of production is at the 19m of this factory ³Blast furnace begins to drop into above-mentioned chromium, nickel, titanium, the vanadium slag agglomerate of containing, useless chemical fertilizer catalyst particle, coal gangue etc., and bosh " displacement " finishes, and above-mentioned agglomerate and useless chemical fertilizer catalyst incorporation be greater than 50%, produces to be in and carry out under the normally stable situation.Flue gas, flue dust are respectively taken a sample 8-9 time, finish (because of this technology continuous and stable production, the reinforced no tangible production cycle property of slagging tap continuously is so be sampled as stochastic sampling in the production process) respectively in continuous two days.The sample collection frequency of ash, slag, water is with before changing the line of production.

(6) test result:

This tests whole results test result table look-up before and after edit is listed in the operation of Xiyang County improvement chromium slag factory " in, each measured value of gravitational dust, sack dust, chimney soot and Water Quenching Slag is two samples making in two days, does two parallel samples, the mean value of four measured values respectively in the table.Detailed data sees Table 6.

After table 6 is seen literary composition

(7) conclusion:

1, from test result, change the line of production before and after under the ordinary production situation in the flue dust chromic content be respectively 0.011mg/Ndm ³And 0.012mg/Ndm ³(with CrO ₃Meter) obviously do not increase phenomenon; Chromic content is respectively 0.012 and 0.014mg/Ndm in the flue gas ³The two basically identical.Do not see the emission standard of chromium in relevant flue dust, the flue gas at present both at home and abroad as yet, only in TJ-36-79 " Design of Industrial Enterprises hygienic standard ", stipulate objectionable impurities chromium trioxide, chromic salt etc. in the workshop air) (with CrO ₃Meter) be that maximum permissible concentration is 0.05mg/Ndm ³With reference to this standard, chromium content all is up to specification in dirt that this factory discharges fume, the flue gas.

2, in the water system, no matter before supplementary feed is changed the line of production or after changing the line of production, Cr wherein ^{+ 6}Content all fails to detect, and concentration is less than 0.004mg/I, its Cr before and after cooling circulating water is changed the line of production in the production process ^{+ 6}Content is respectively 0.006mg/I and 0.010mg/I does not have considerable change; The pulp water of quenching in the production process, Cr before and after it is changed the line of production ⁶⁺Content be respectively 0.006mg/I and 0.008mg/I, do not have considerable change yet.Cr in three kinds of water ⁶⁺Content all is lower than GB8978-88 " integrated wastewater discharge standard " first kind pollutent Cr ⁶⁺The highest permission emission concentration value 0.5mg/I.

3, the Top of BF flue gas of discharging passes through gravitational precipitator respectively, ashes that sack cleaner gets and the aggegation sedimentation of chimney internal cause and chimney soot, its water-solubility Cr before changing the line of production ⁶⁺Content difference＜0.04mg/Kg,＜0.04mg/Kg and 0.049mg/Kg, change the line of production the back its water-solubility Cr ⁶⁺Content be respectively 0.04mg/Kg, 0.04mg/Kg and 0.051mg/Kg, content basically identical before and after various ashes are changed the line of production does not have considerable change.From numerical value, Cr in the various ash discharges ⁶⁺Content all in the trace content range.

Become granulated bf slag after the water quenched slag that discharge the body of heater bottom, its water-solubility Cr before and after this slag is changed the line of production ⁶⁺Content respectively 0.05mg/Kg and 0.06mg/Kg, both do not have considerable change, and all far below the prescribed value 1.5mg/l among the GB5805-85 " non-ferrous metals industry solid waste leach liquor toxicity judging standard ".

4, utilize this Technology to carry out this project and administer Cr in the various in process of production discharges ⁶⁺Content very little, can not cause secondary pollution, we can say that this technology can reach the effect completely of detoxifying to the processing that above-mentioned nuisance contains chromium, nickel, titanium, vanadium waste residue.

Embodiment

Embodiment 1:

(1) gets the raw materials ready: contain waste residue agglomerates such as chromium, nickel, useless chemical fertilizer catalyst particle, coal gangue, coke (can the calorific value height, the standard compliant total coke of thermostability be that the anthracite block coal of 1/4-1/2 substitutes), lime or Wingdale and fluorite is broken respectively, screening is the 15-50 mm particle size with above-mentioned, by quaternary basicity (CaO+MgO)/(SiO ₂+ Al ₂O ₃) 0.85-1.25; Dual alkalinity (CaO/SiO ₂) be controlled at 0.95-1.35 and prepare burden.

(2) batching: go in the high furnace charge above-mentioned agglomerate: useless chemical fertilizer catalyst particle and/or coal gangue: coke (with (1), slightly): lime or Wingdale: fluorite=8-40%: 8-40%: 10-15%: 20-35%: 20-35%(is in lime): 1-2%.

Above-mentioned agglomerate and/or useless chemical fertilizer catalyst particle: coal gangue: coke (with (1), slightly): lime or Wingdale: fluorite=20-50%: 10-18%: 20-40%: 16-36%(is in lime): 1-2.5%.

Going into furnace charge by batching, present embodiment criticizes and is: 245 kilograms of above-mentioned agglomerates, 10 kilograms of useless chemical fertilizer catalyst particles, 90 kilograms of coal gangues, 160 kilograms in lime, 140 kilograms in coke (with (1), slightly), 8 kilograms in fluorite.

(3) blast-furnace smelting: former, the auxilliary fuel that will prepare drops in the blast furnace 2, and the processing condition of blast-furnace smelting are:

Blast furnace blast amount 100-140 rice ³/ minute;

Cold wind pressure 320-560 mmhg;

Hot blast temperature 950-1100 ℃;

Throat temperature is controlled at 200-300 ℃;

Shrend water pressure 0.3-0.6Mpa;

The shrend water temp is less than 60 ℃;

Slag iron is than 1.5-6.0 Water Quenching Slag ton/contain pig iron tons such as chromium, nickel;

System slag coke ratio 300-550 coke kilogram/Water Quenching Slag ton;

Coke load 2.0-3.8 goes into stove ore deposit ton/coke ton;

The about 1450-1650 of temperature of the furnace hearth ℃

The about 1450-1480 of slag notch temperature ℃.

(4) technical process: former, auxilliary, fuel dropped in the blast furnace by blast-furnace burden smelt,, begin to feed in raw material 19 meters when furnace charge drops to the stockline position when following ³Added a defective material in the general 10-15 of small furnace minute, continuous charging, interruption discharging.Smelt by aforementioned processing condition, carry out suitability for industrialized production, can obtain containing Cr, Ni, Ti, Mn, Si, the V pig iron along accompanying drawing 1 technical process; Granulated bf slag can be prepared holllow building block, cement and other building material made.

Institute's column data can be found out from table 9,10, does the cement additive test with this Water Quenching Slag 30-40%, proves that it is the high-quality active addition of cement, can produce the 325-525# Portland blast.Facts have proved that its suitable incorporation is 30-40%.Simultaneously, increase calcium slag, coal gangue and cement clinker with Taiyuan Iron and Steel Co. Water Quenching Slag, 541 and done contrast.

Embodiment 2, go into furnace charge and criticize and be:

230 kilograms of useless chemical fertilizer catalyst particles, 150 kilograms in lime, 82 kilograms of coal gangues, coke (with (1), slightly), 180 kilograms, 8 kilograms in fluorite.

Embodiment 3, go into furnace charge and criticize and be:

260 kilograms of above-mentioned agglomerates, 90 kilograms of coal gangues, 150 kilograms in coke (with (1), slightly), 170 kilograms in lime, 10 kilograms in fluorite.

Table 5: above-mentioned chromium residue sintering lump ore is formed (weight %)

Preface is formed (weight %)

Preface Cr ₂O ₃NiO TiO ₂MnO Fe ₂O ₃Al ₂O ₃CaO MgO SiO ₂

1????4.14????2.71????0.40????0.39????7.81????9.52????30.38????8.17????20.29

2????2.64????3.47????0.47????0.41????20.10????10.73????20.15????10.89????24.18

3????4.29????0.59????0.58????0.17????11.50????13.25????22.08????16.70????24.34

4????4.65????2.69????0.57????0.31????10.59????11.60????23.29????19.41????24.93

5????15.89????2.97????0.58????0.23????19.57????23.37????20.10????10.51????27.13

6????7.28????1.37????0.76????0.33????11.65????8.98????27.65????18.15????6.55

7????5.56????1.87????0.77????0.43????14.20????7.95????29.77????18.64????7.30

Table 6: chromium slag factory operation front and back test result table look-up is administered in the Xiyang County

Measured value remarks after measured value was changed the line of production before sample was surveyed and changed the line of production

The product examination

Name Xiang Xu measured value average preface measured value preface measured value average

Claim order number number number

Cr????1????0.004????1????0.008????6????0.004

Cigarette 2 0.009 2 0.004 7 0.008

（mg/Ndm）????3????0.004????0.0057????3????0.008????8????0.008????0.0062

Dirt 44 0.004 9 0.004

5????5????0.008????10

Cigarette Cr 1 0.003 1 0.016 5 0.016

2????0.013????2????0.017????6????0.011

0.0123????0.0139

Gas (mg/Ndm) 3 0.014 3 0.017 7 0.015

4????0.019????4????0.016????8????0.003

Mend Cr 1＜0.004 1＜0.004 4＜0.004

Give 2＜0.004＜0.004 2＜0.004 5＜0.004＜0.004

Water (mg/L) 3＜0.004 3＜0.004 6＜0.004

Follow Cr 1 0.009 1 0.004 4 0.016

Encircle 2 0.004 0.006 2 0.008 5 0.016

Water (mg/L) 3 0.005 3 0.012 6

Cr 1 0.010 1 0.014 4 quenches

Slag 2 0.005 0.006 2 0.005 5 0.008

Water (mg/L) 3 0.004 3 0.010 6

Heavy Cr water

Power＜0.04 0.04 is molten

Ash (mg/kg) property

Cloth Cr water

Bag＜0.04 0.04 is molten

Ash (mg/kg) property

Cigarette Cr water

Chimney 0.049 0.051 is molten

Ash (mg/kg) property

Water Cr water

It is 0.05 0.08 molten to quench

Slag (mg/kg) property

Table 10: cement mortar strength test result

Numbering mixing material folding strength MPa ultimate compression strength MPa remarks

Kind volume % 3 days 7 days 28 days 90 days 3 days 7 days 28 days 90 days

Contain chromium water

I-1-2 slag 35 5.3 5.7 7.6 8.6 20.0 24.0 55.5 62.4 material fineness % that quench

I-2-2 〃 〃 4.9 5.5 7.8 9.9 21.2 28.9 51.6 67.2 is with table

Ⅱ-1-2????〃????〃????5.0????5.9????7.8????9.4????22.3????30.8????49.9????64.7

Ⅱ-2-2????〃????〃????4.8????5.4????7.4????8.5????20.7????26.4????48.0????64.0

Ⅲ-1-2????〃????〃????4.6????5.5????7.5????8.7????20.0????26.7????44.5????60.8

Ⅲ-2-2????〃????〃????4.5????5.6????7.8????8.6????18.3????27.6????46.4????62.3

Taiyuan Iron and Steel Co.

4 grain slag 〃 4.8 5.7 7.4 8.7 19.2 23.7 47.9 61.5

5????541????〃????4.9????5.6????7.2????7.3????22.2????28.2????49.7????60.4

Increase the calcium slag

6 coal gangue 〃 4.8 5.4 7.1 8.0 21.3 27.7 42.6 55.9

Contain chromium water

I-1-3 slag volume % 4.4 5.6 6.8 9.0 19.2 28.6 53.6 69.1 material fineness % that quench

I-2-3 〃 40 4.1 5.5 7.5 8.8 17.5 26.2 53.8 66.7 is with table

II-1-3 〃 〃 4.4 5.4 7.5 8.2 17.5 25.7 49.1 67.5 initial set 4:27 final set 5:57

Ⅱ-2-3????〃????〃????4.2????4.6????7.5????7.8????17.6????23.6????48.3????59.9

Initial set was coagulated 5: 23 eventually at 3: 38

Ⅲ-1-3????〃????〃????4.2????4.6????7.6????8.1????18.2????21.6????40.6????56.9

Ⅲ-2-3????〃????〃????3.7????4.3????7.1????8.3????16.0????22.0????42.4????56.7

7 Taiyuan Iron and Steel Co.s

Grain slag 〃 4.2 5.1 6.6 8.5 18.4 24.4 45.8 59.5

8????541????〃????4.3????4.9????6.5????7.2????17.0????26.0????42.7????55.1

Increase the calcium slag

9 coal gangue 〃 4.1 4.8 7.3 7.3 17.6 24.0 45.2 46.3

Cement clinker does not have 7.5 7.7 8.5 60 days 36.1 44.2 55.3 60 days

9.2????60.2

Claims (8)

1; a kind of radical cure vanadium and hexavalent chromium polluted; to containing chromium; nickel; titanium; vanadium; manganese; the iron chemical fertilizer catalyst that gives up; contain chromium; nickel electrodeposited chromium mud; stainless steel grinding dust dirt; the coal gangue waste carries out high-temperature fusion and smelts; thoroughly detoxifcation; the novel process of non-secondary pollution and comprehensive utilization; it is characterized in that: the chemical fertilizer catalyst that will give up sieves; make its powder and contain chromium; nickel electrodeposited chromium mud; stainless steel grinding dust dirt; pulverized anthracite or coke powder are former; fuel; be equipped with red clay or bauxitic clay; kaolin; adopt sintering process that its sintering is made the sintering lump ore; with this sintering lump ore and/or useless chemical fertilizer catalyst particle is main raw material; with bastard coal masonry auxiliary material; make fuel and reductive agent with coke; add lime or Wingdale; fluorite is a flux; prepare burden; directly into blast-furnace smelting, in blast furnace, through the pyrocarbon thermal reduction; the fusion detoxifcation; layering separates; the iron notch output contains Cr; Ni; Ti; Mn; the V pig iron, slag notch must can be used as the granulated bf slag of producing the building materials raw material through shrend.

2, detoxifcation according to claim 1 is smelted and is contained Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process, and the proportioning raw materials when it is characterized in that sintering (weight %) is: useless chemical fertilizer catalyst powder: contain chromium, nickel electrodeposited chromium mud: stainless steel grinding dust dirt: pulverized anthracite or coke powder: red clay or bauxitic clay, kaolin=1-30%: 1-15%: 20-60%: 10-30%: 10-25%.

3, detoxifcation according to claim 1 is smelted and is contained Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process, and the proportioning raw materials when it is characterized in that sintering (weight %) is: useless chemical fertilizer catalyst powder and/or stainless steel grinding dust dirt: contain chromium, nickel electrodeposited chromium mud: coke powder or pulverized anthracite: red clay or aluminium vanadine, kaolin=20-65%: 1-20%: 10-30%: 10-30%.

4, detoxifcation according to claim 1, smelt and to contain Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process, proportion of raw materials when it is characterized in that sintering (weight %) is: useless chemical fertilizer catalyst powder and/or contain chromium, nickel electrodeposited chromium mud: stainless steel grinding dust soil: pulverized anthracite or coke powder: red clay or aluminium vanadine, kaolin=20-40%: 6-30%: 10-30%: 10-25%.

5, detoxifcation according to claim 1 is smelted and is contained Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process, it is characterized in that said useless chemical fertilizer catalyst is to be used in chemical fertilizer, sulfuric acid, methanation, hydrogenation, the conversion production process mainly to contain Cr, Ni, Ti, V, Fe, K ₂O, Na ₂The multiple chemical fertilizer catalyst that the O composition is different, the useless chemical fertilizer catalyst through poisoning, wearing out, lost efficacy and form;

Said stainless steel grinding dust dirt is the dust that mainly contains Cr, Ni, Ti, Mn, Fe composition of stainless steel factory or the discharge of Stainless Steel Products factory, the solid waste of considering grain to be worth doing, cutting slag, iron scale;

6, detoxifcation according to claim 1 is smelted and is contained Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process, it is characterized in that blast-furnace burden, and its ratio of components (weight %) is:

(1), 9 * 8 millimeters useless chemical fertilizer of the about Φ of above-mentioned agglomerate and/or granularity are urged the agent particle: coal gangue: coke: lime or Wingdale: fluorite=20-50%: 10-18%: 20-40%: 18-35%(is in lime): 1-2.5%.

(2), blast-furnace burden quaternary basicity (CaO+MgO)/(SiO ₂+ Al ₂O ₃) be 0.85-1.25, dual alkalinity CaO/SiO ₂Be controlled at 0.95-1.35.

(3), coke substitutes with the anthracite block coal of the 1/4-1/2 of calorific value height, the total consumption of the standard compliant coke of thermostability.

7, detoxifcation according to claim 1 is smelted and is contained Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process, it is characterized in that the main technologic parameters when blast furnace is produced is:

(1), blast furnace blast amount 100-140 rice ³/ minute;

(2), cold wind pressure 320-560 mmhg;

(3), hot blast temperature 950-1100 ℃;

(4), throat temperature is controlled at 200-300 ℃;

(5), shrend water pressure 0.3-0.6MPa;

(6), the shrend water temp is less than 60 ℃;

(7), slag iron is than 1.5-6.0 Water Quenching Slag ton/contain pig iron tons such as chromium, nickel;

(8), system slag coke ratio 300-550 coke kilogram/Water Quenching Slag ton;

(9), coke load 2.0-3.8 goes into stove ore deposit ton/coke ton.

8, detoxifcation according to claim 1 is smelted and is contained Cr, Ni, Ti, Mn, the V pig iron and comprehensive utilization novel process; symmetric double slag notch when it is characterized in that blast furnace production; with pressure water shrend flushing cinder, obtain the granulated bf slag that quality satisfies system building materials ingredient requirement.

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