WO2020015382A1 - 一种含硫矿物改性硅酸盐水泥熟料的生产方法 - Google Patents

一种含硫矿物改性硅酸盐水泥熟料的生产方法 Download PDF

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WO2020015382A1
WO2020015382A1 PCT/CN2019/080472 CN2019080472W WO2020015382A1 WO 2020015382 A1 WO2020015382 A1 WO 2020015382A1 CN 2019080472 W CN2019080472 W CN 2019080472W WO 2020015382 A1 WO2020015382 A1 WO 2020015382A1
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cement
clinker
mortar
modified
kiln
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PCT/CN2019/080472
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English (en)
French (fr)
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马素花
李伟峰
时斐
沈晓冬
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南京工业大学
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/02—Portland cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/246—Cements from oil shales, residues or waste other than slag from waste building materials, e.g. waste asbestos-cement products, demolition waste
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/421—Inorganic materials
    • C04B7/427—Silicates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the invention belongs to the field of building materials, and relates to a method for producing sulfur-containing mineral-modified portland cement clinker, in particular to the application of cement hardened mortar in waste concrete in the production of the cement clinker.
  • the calcium sulphoaluminate modified portland cement (SMP) has the advantages of fast hydration and hardening, high early strength and micro-expansion.
  • SMP calcium sulphoaluminate modified portland cement
  • the existing technology and research are mainly through adjusting the production process parameters (such as adjusting the raw material ratio or adding ore). Chemical agents, etc.) or change the production process (such as the use of secondary firing, etc.) to achieve the above purpose.
  • Chinese invention patent ZL200910212645.0 discloses an improved calcination process of introducing early-strength calcium sulphoaluminate mineral into Portland cement clinker, that is, by mixing gypsum into cement raw material and adjusting the thermal process of calcining the clinker.
  • System (such as heating, heat preservation, and cooling rate) to achieve the secondary synthesis of calcium sulfoaluminate mineral in Portland cement clinker, thereby improving the early strength of cement clinker.
  • the technical scheme of secondary synthesis of calcium sulphoaluminate mineral in cement clinker is achieved through technical measures such as heat treatment. It is difficult to control the parameters in actual industrial production applications. It is even necessary to modify the existing production process equipment and process technology.
  • Chinese invention patent ZL200710118915.2 discloses a post-firing process for high-performance cement clinker. A certain amount of calcium sulfate particles are sprayed through the high-temperature zone, the front cooling zone or the post-cooling zone of the clinker fired in a rotary kiln , Producing early-strength Portland cement clinker containing calcium sulphoaluminate.
  • the clinker temperature in this section of the kiln starts to decrease, and the amount of liquid phase gradually decreases.
  • Some clinker mineral phases such as Belite may also be wrapped by the liquid phase, which affects the injected calcium sulfate particles and Quick response.
  • mineralizers such as calcium sulfate can cause caking, crusting, etc. that affect the operation and stable operation of the kiln.
  • invention patent 201510946574.2 discloses a cement kiln bypass venting combined staged combustion kiln tail flue gas treatment device and process method to improve a series of problems caused by excessive potassium, sodium, chlorine and sulfur circulation in the kiln.
  • the existing technology adopts technical measures such as bypass air release, reducing sulfur volatilization, and controlling sulfur condensation position.
  • Invention patent 201510033679.9 discloses a method for vapor phase synthesis of calcium sulphoaluminate modified portland cement clinker. The method utilizes vapor phase SO 2 and CaO in freshly burned mature material to generate highly active CaSO 4 , and newly formed CaSO 4 and The solid phase reaction of C 3 A in clinker forms calcium sulphoaluminate. This provides a reference for the improvement of sulfur cycle in rotary kiln.
  • the main technical problem to be solved by the present invention is to provide a method for producing a sulfur-containing mineral modified portland cement clinker, in particular to the application of cement hardened mortar in waste concrete in the production of the cement clinker.
  • a method for improving the sulfur cycle caused by the decomposition of sulfate in the high temperature section of the rotary kiln is also provided.
  • the cement hardened mortar fine powder particles sprayed at the kiln head position will quickly dehydrate after high temperature flue gas and form light particles with high activity and high specific surface area (including active CaO). It reacts with a part of the SO 2 that escapes from the decomposition of sulfate and precipitates sulfur.
  • the basic idea of the present invention is: a certain amount of modification is injected from the position of the kiln head of the rotary kiln without changing the firing conditions of Portland cement clinker in the new dry process kiln.
  • Cement hardened mortar fine powder Modified cement mortar fine powder quickly dehydrates when exposed to high temperature flue gas and forms light particles with high activity and high specific surface area (including active CaO, dehydrated CSH, etc.), which is brought into the high temperature section by the secondary air and reacts with sulfuric acid Part of the SO 2 reacted by the salt decomposition reacts, and CaSO 4 is regenerated and settled into the calcined portland cement clinker at the position of the rear high temperature zone or the front cooling zone.
  • the unreacted components in the fine powder of modified cement hardened mortar are thermally decomposed during the sedimentation process, such as CSH dehydration and decomposition to C 2 S, sulfur-containing hydration product Aft / AFm dehydration and decomposition to CaSO 4 and so on.
  • Neonatal having high reactivity CaSO 4 can clinker with C 2 S (in particular, a modified powder The new C 2 S) and C 3 A / C 4 AF formed by dehydration and decomposition of CSH during the secondary high-temperature section and the front cooling zone undergo secondary solid-phase reaction to form calcium sulfosilicate (2C 2 S.CaSO 4 ) and aluminum sulfide.
  • C 2 S in particular, a modified powder
  • C 3 A / C 4 AF formed by dehydration and decomposition of CSH during the secondary high-temperature section and the front cooling zone undergo secondary solid-phase reaction to form calcium sulfosilicate (2C 2 S.CaSO 4 ) and aluminum sulfide.
  • a method for producing a sulfur-containing mineral modified portland cement clinker characterized in that modified cement hardened mortar fine powder is added into the kiln from a kiln head position of a new dry-type rotary kiln by using a coal injection pipe; At high temperature, the flue gas dehydrates and forms light particles with high activity and high specific surface area (including active CaO, dehydrated CSH, etc.). It forms new CaSO 4 through gas-solid reaction with SO 2 produced by the decomposition of sulfate in the high temperature section, and settles to mature.
  • the modified cement hardened mortar fine powder is prepared by the following methods: the hardened cement mortar obtained by crushing the waste concrete and separating the coarse aggregate, then adding a liquid auxiliary during the grinding process to modify the surface of the powder, and finally selecting the powder After the siliceous fine aggregate (generally quartz sand) is separated, the modified cement hardened mortar fine powder mainly composed of active calcium hydroxide (CH), hydrated calcium silicate (CSH) and the like is obtained.
  • CH active calcium hydroxide
  • CSH hydrated calcium silicate
  • the above sulfur-containing minerals are calcium thiosilicate (2C 2 S. CaSO 4 ) and calcium thioaluminate Sulfur-containing mineral modified Portland cement clinker refers to Multi-mineral composite Portland cement clinker.
  • the above-mentioned modified cement hardened mortar fine powder is an organically modified mixed powder mainly composed of active calcium hydroxide (CH), hydrated calcium silicate (C-S-H), and a small amount of aluminum-containing hydration products (Aft and AFm).
  • the milling equipment used for the milling is a ball mill or a vertical mill.
  • the liquid auxiliary is an aqueous solution of a polyhydric alcohol, and the mass concentration of the solute in the aqueous solution ranges from 30% to 60%.
  • the polyhydric alcohol is an aqueous solution of any one or more of ethylene glycol (EG), diethylene glycol (DG), 1,2-propylene glycol (MPD) or glycerol.
  • EG ethylene glycol
  • DG diethylene glycol
  • MPD 1,2-propylene glycol
  • glycerol aqueous solution of any one or more of ethylene glycol (EG), diethylene glycol (DG), 1,2-propylene glycol (MPD) or glycerol.
  • the amount of the liquid auxiliary is 0.03 to 0.08% of the mass of the hardened cement mortar.
  • the 80 um sieve balance of the modified cement hardened mortar fine powder is 1.0 to 3.0%.
  • the modified cement hardened mortar fine powder is added into the kiln in an amount of 2-10% of the mass of the raw material feed.
  • the present invention provides a method for producing a sulfur-containing mineral modified Portland cement clinker, and particularly relates to the application of cement hardened mortar in waste concrete in the production of the cement clinker.
  • a method for producing a sulfur-containing mineral modified Portland cement clinker Including: firstly crushing the waste concrete and separating the coarse aggregate, the hardened cement mortar is obtained by grinding, selecting powder, adding a liquid auxiliary during the grinding process to chemically modify the surface of the powder, and separating the silicon through a powder selecting device Fine aggregate (quartz sand) to obtain modified cement hardened mortar fine powder; adding the modified cement hardened mortar fine powder from the kiln head position of the new dry-type rotary kiln into the kiln by using coal injection pipe, and finally obtaining sulfur-containing minerals Modified Portland cement clinker.
  • Fine aggregate limestone sand
  • the calcium hydroxide (CH) and hydrated calcium silicate (CSH) in the fine powder are rapidly dehydrated to form a new activity.
  • the dehydrated fine powder has the characteristics of high specific surface area, porosity, light weight, etc., and is easily carried into the rear high temperature section of the rotary kiln by the secondary air.
  • the newly generated active CaO in the fine powder reacts with part of the SO 2 decomposed by the sulfate decomposition in the clinker to form CaSO 4 and settle into the clinker (the incompletely reacted active CaO is not dense CaO because it has not been sintered at high temperature. Not only does it not affect the stability of the cement, but it can increase the initial alkalinity and promote the hydration of the cement); and the Portland cement clinker in this section (the location of the rear high temperature zone or the front cooling zone) has been fired.
  • the clinker can A large amount of C 2 S (especially the newly generated high activity C 2 S formed by dehydration and decomposition of CSH in fine powder) and C 3 A / C 4 AF form sulfur through secondary solid-phase reaction in the rear high temperature section and the front cooling zone. Calcium silicate and calcium sulphoaluminate are finally removed from the kiln with clinker to obtain Multi-mineral composite Portland cement clinker.
  • Calcium thiosilicate (2C 2 S.CaSO 4 ) is an intermediate mineral in the calcination process of Portland cement clinker and sulphoaluminate cement clinker with high sulfur content: when the calcination temperature is between 900 and 1200 ° C In the range, Belite and anhydrite react to form calcium thiosilicate and stably exist; when the calcination temperature exceeds 1200 ° C, calcium thiosilicate will be decomposed into Belite and anhydrite again.
  • WO2013023728 A3 discloses a thioaluminate cement clinker containing sulfosilicate and a method for preparing the same, and the application of the clinker as an additive of the sulfoaluminate cement.
  • the Chinese invention patent with the application number of 201711222374.8 discloses a method for modifying a sulfoaluminate cement by using a calcium sulfosilicate mineral, which improves the post-strength of the sulfoaluminate and improves the post-stage shrinkage.
  • the calcium silicate hydrate powder in the hardened cement mortar through (CSH) into the kiln dehydration, decomposition of C 2 S is produced, which is high temperature sintering reactivity than the original clinker C 2 S (Yang Nanru, Zhong Baiqian. Study of active ⁇ -C 2 S.
  • the newly generated CaSO 4 with high reactivity and a large amount of clinker C 2 S, especially the newly generated and highly active C 2 S formed by dehydration and decomposition of hydrated calcium silicate (CSH) in fine powder forms calcium sulfosilicate (2C 2 S.CaSO 4 ) through solid phase reaction; this interval
  • the temperature of the segment (the position of the rear high temperature zone or the front cooling zone) is favorable for the formation and stable existence of calcium sulfosilicate (2C 2 S.CaSO 4 ).
  • the later high temperature section and the front cooling zone section are also conducive to the solid phase reaction of the C 3 A / C 4 AF minerals present in the raw clinker with the new CaSO 4 solid phase to form calcium sulfoaluminate. mineral.
  • the hardened cement mortar is pre-milled and powder-selected, and a liquid auxiliary is added to the powder during the milling process to chemically modify the surface of the powder, and the siliceous fine aggregate (quartz sand) is separated by a powder-selection device. ), And further obtain a modified cement hardened mortar fine powder.
  • the purpose of grinding is to increase the specific surface area of the fine powder that can participate in the chemical reaction, so as to speed up the rate of various chemical reactions such as dehydration, sulfur fixation and solid phase reaction after entering the kiln; the polyol is mainly used during the grinding process.
  • the liquid auxiliary of the component chemically modifies the surface of the powder.
  • the liquid auxiliary uses a polyhydric polyol as a main component, and is added in the grinding process to aid grinding and dispersion, thereby improving the grinding efficiency. And optimize the particle distribution;
  • the uniform distribution of the liquid additive on the surface of the powder changes the gas-solid two-phase surface properties of the powder, and significantly improves the degree of dispersion of the liquid into the kiln, which is beneficial to Heat exchange and gas-solid reaction with SO 2 in the flue gas proceed.
  • Quartz sand in cement hardened mortar has high crystallinity, which affects the abrasiveness of clinker.
  • the sand separation principle of the powder separator is used as the recycled fine aggregate (RFA) to avoid the index of clinker abrasiveness and insoluble matter of quartz sand with high crystallinity. Impact.
  • the present invention has a simple process, a short process, and is easy to promote.
  • the modified cement is sprayed into the kiln head.
  • the fine powder of hardened mortar achieves the solidification of part of SO 2 and the improvement of the sulfur cycle that escape from the sulfate decomposition in the high temperature zone in the rotary kiln through the gas-solid reaction process; on the other hand, it uses the gas-solid reaction and sulfur-containing hydration respectively.
  • the fresh CaSO 4 generated by the dehydration of the product and the active C 2 S generated by the decomposition of CSH, and the secondary solid phase reaction generates calcium sulfosilicate and calcium sulfoaluminate minerals, achieving Firing of multiphase composite clinker system.
  • Another beneficial effect of the present invention is that without substantially increasing the load and energy consumption of the kiln system, an increase in clinker production is achieved, and energy consumption per ton of clinker is reduced.
  • the hardened cement mortar used in Example 1 was taken from a waste concrete production recycled coarse aggregate (RCA) factory A. It is a fine-grained part after separation of RCA (0.2mm sieve residue ⁇ 25%, water content 1.5%), mainly Hardened cement mortar with a small amount of clay impurities.
  • the hardened cement mortar was pulverized with a ball mill, and siliceous quartz sand was selected and separated to obtain fine powder of modified cement hardened mortar (80um sieve balance 2.1%, water content 1.4%), which was homogenized in the warehouse for future use.
  • a 0.05% liquid auxiliary is added, which is a 45% ethylene glycol (EG) aqueous solution with a mass concentration.
  • a certain 2500t / d new-type dry-process cement clinker production line in the southwest (rotary kiln specifications: ⁇ 4m ⁇ 60m, slope 4%, MFC-type decomposition furnace and five-stage suspension preheater, third-generation TC-type inflatable beam grate cooler)
  • the modified cement hardened mortar fine powder of this embodiment is added into the kiln through a coal injection pipe at the kiln head position according to 5.5% of the raw material input into the kiln to produce the sulfur-containing mineral modified portland cement clinker of the present invention. Kiln output increased by about 3.8%.
  • the early strength and late strength of the cement clinker obtained by applying the technology of the embodiment of the present invention are significantly improved compared with the strength of the clinker before application;
  • the free calcium f-CaO in the chemical indicators increased slightly, mainly modified cement hardened mortar fine powder It is caused by the incomplete reaction of CaO in the medium, but has no effect on the stability (qualified);
  • the insoluble matter content has increased slightly, which may be related to the small amount of quartz sand sandwiched;
  • the increase in the SO 3 content in the clinker is mainly due to sulfur fixation It is related to the gypsum brought by the fine powder of modified cement hardened mortar;
  • the setting time (initial and final setting) is slightly shortened.
  • the clinker performance is significantly improved.
  • the indicators of f-CaO, insoluble matter, and SO3 have increased in detail, it does not affect the stability and strength properties of the clinker.
  • the hardened cement mortar used in Example 2 was taken from a waste concrete production recycled coarse aggregate (RCA) factory B. It was a block and powdered hardened cement mortar mixture after separating RCA (0.2mm sieve ⁇ 35%, containing Water content is 2.3%), and the content of broken bricks and tiles is about 3.2%.
  • the block-hardened cement mortar was pre-crushed, dried by a vertical mill, the hardened cement mortar was milled, and siliceous quartz sand was separated to obtain fine powder of modified cement hardened mortar (80um sieve balance 2.8%, water content 0.8%). ), Homogenized for storage.
  • a 0.08% liquid auxiliary is added during the grinding process, which is a mixed aqueous solution of diethylene glycol (EG) and glycerol with a mass concentration of 32%, wherein the mass ratio of diethylene glycol and glycerol is 12:20.
  • EG diethylene glycol
  • glycerol a mixed aqueous solution of diethylene glycol (EG) and glycerol with a mass concentration of 32%, wherein the mass ratio of diethylene glycol and glycerol is 12:20.
  • the modified cement hardened mortar fine powder of this embodiment is added into the kiln through a coal injection pipe at the kiln head position according to 2.5% of the raw material input into the kiln to produce the sulfur-containing mineral modified portland cement clinker of the present invention.
  • Kiln output increased by about 2%.
  • the hardened cement mortar used in Example 3 was taken from a waste concrete production recycled coarse aggregate (RCA) factory C. It is a powdered hardened cement mortar after RCA separation (0.2mm sieve ⁇ 18%, moisture content 2.8%) , With a small amount of broken bricks, tiles, clay and other impurities ( ⁇ 1%).
  • the powdery hardened cement mortar is pre-dried, the hardened cement mortar is ground with a ball abrasive, and the siliceous quartz sand is separated to obtain a modified cement hardened mortar fine powder (80um sieve balance 1.1%, water content 1.0%)
  • the library is homogenized for future use.
  • liquid auxiliary is added in the grinding process, which is a mixed aqueous solution of propylene glycol, diethylene glycol and glycerin with a mass concentration of 60%, wherein the mass ratio of propylene glycol, diethylene glycol and glycerol is 1: 1: 1.
  • a 5000t / d new-type dry-process cement clinker production line in Anhui (the size of the rotary kiln is ⁇ 5.2m ⁇ 61m, a TDF type decomposition furnace and a five-stage suspension preheater, and a third-generation TC-type controllable airflow grate cooler).
  • the modified cement hardened mortar fine powder of this embodiment was added into the kiln through a coal injection pipe at the kiln head position according to 8.5% of the raw material amount into the kiln to produce the sulfur-containing mineral modified portland cement clinker of the present invention.
  • Kiln output increased by about 6.6%.
  • both the early strength and the later strength of the cement clinker obtained by applying the technology of the embodiment of the present invention are significantly improved compared to the clinker strength before application, in which the 3d compressive strength increased by 1.3Mpa and 28d compressive strength increased by 3.5Mpa; Free calcium f-CaO increased in detail, reaching 1.4 to 1.8% (the upper limit has exceeded the GB / T21372-2008 index ⁇ 1.5%), which is mainly caused by the decomposition of calcium hydroxide carried by the fine powder of modified cement hardened mortar into active CaO Because it is a non-dense CaO that has not been sintered at high temperature, it does not affect the stability of the cement, but can increase the initial alkalinity and promote the hydration of the cement.
  • the insoluble matter content has increased slightly, which may be related to the small amount of quartz sand sandwiched.
  • the increase of SO 3 content in the material is obvious, mainly due to sulphur fixation and gypsum brought by the fine powder of modified cement hardened mortar; the setting time (initial and final setting) is slightly shortened. From the above point of view, after adopting Example 3 of the present invention, the clinker performance is improved. Although the indicators such as f-CaO, insoluble matter, and SO 3 have increased in detail, it does not affect the stability and strength properties of the clinker.

Abstract

一种含硫矿物改性硅酸盐水泥熟料的生产方法，将改性水泥硬化砂浆微粉，从干法回转窑的窑头位置利用喷煤管向窑内加入，最终获得一种含硫矿物改性的硅酸盐水泥熟料；其中改性水泥硬化砂浆微粉是将废弃混凝土破碎、分离粗骨料后得到的硬化水泥砂浆，然后在粉磨硬化水泥砂浆过程中加入液体助剂对粉体进行表面改性，选粉后获得。以废弃混凝土中的水泥硬化砂浆为主原料，一方面通过气固反应实现了回转窑中的硫循环改善；另一方面通过二次固相反应生成硫硅酸钙和硫铝酸钙矿物，实现多相复合熟料体系的烧成。

Description

一种含硫矿物改性硅酸盐水泥熟料的生产方法 技术领域
本发明属于建筑材料领域，涉及一种含硫矿物改性硅酸盐水泥熟料的生产方法，尤其涉及废弃混凝土中的水泥硬化砂浆在该水泥熟料生产中的应用。
背景技术
我国是水泥生产大国，2017年全国水泥产量达23.16亿吨。水泥工业能耗高、资源消耗大、环境污染重，而能源、资源消耗和环境污染主要集中于水泥生产的熟料烧成工艺段。因此，熟料烧成工艺的进步革新主要集中于节能和减排两个方面：节能，即采用低能耗熟料烧成技术，通过技术改进或采用节能装备降低吨熟料的烧成煤耗、电耗及CO 2排放量；减排，即采用低大气污染物(如SO 2、NO x等)及低CO 2排放的烧成技术或装备。其中，通过在传统硅酸盐水泥矿相体系中引入其它矿物组成(如硫铝酸钙、硫硅酸钙等)以制备高强度熟料，从而减少吨水泥生产中的熟料用量(或增加粉煤灰、矿渣等混合材的掺入量)，是当前水泥工业实现节能减排及可持续发展的重要途径之一。
硫铝酸钙改性硅酸盐水泥(SMP)兼有水化硬化快、早强高和微膨胀等优点，但同时硫铝酸钙改性硅酸盐水泥熟料的生产及应用还存在一些问题。一方面，由于硫铝酸钙和阿利特的共存温度范围不一致，利用新型干法生产线烧成难度较大；现有技术和研究主要是通过调整生产工艺参数(如调整生料配比或加矿化剂等)或改变生产工艺流程(如采用二次烧成等)来实现上述目的。另外一方面，该类型水泥熟料虽然有利于掺如粉煤灰等混合材及早期强度增长，但是其后期强度增进不足甚而存在强度倒缩的情况，限制了该类型水泥的推广和应用(刘晨，王昕,颜碧兰,等.JC/T《硫铝酸钙改性硅酸盐水泥》行业标准介绍.2009,(8):61-64)。
中国发明专利ZL 200910212645.0公开了一种在硅酸盐水泥熟料中引入早强硫铝酸钙矿物的的改进煅烧工艺，即通过在水泥生料中掺入石膏，并调整熟料煅烧的热工制度(如升温、保温及冷却速率等)，来实现硅酸盐水泥熟料中的硫铝酸钙矿物的二次合成，从而提高水泥熟料的早期强度。通过热处理等技术措施来实现水泥熟料中硫铝酸钙矿物二次合成的技术方案，在实际工业生产应用中的参 数控制难度较大，甚而需对现有生产工艺设备进行改造，对工艺技术人员要求也较高。中国发明专利ZL 200710118915.2公开了一种高性能水泥熟料的后烧成的工艺方法，通过在回转窑中熟料烧成的后高温带、前冷却带或后冷却带喷入一定量硫酸钙颗粒，生产含有硫铝酸钙的早强型硅酸盐水泥熟料。但实际上，在窑内这一区间段的熟料温度开始降低，液相量逐渐减少，部分熟料矿相如贝利特等也可能被液相所包裹，从而影响喷入的硫酸钙颗粒与其快速反应。此外，矿化剂如硫酸钙等会导致结圈、结皮等影响窑的操作和稳定运行。
另外一方面，我国绝大部分的水泥企业熟料生产采用新型干法工艺，烧成所用燃料也基本以煤炭为主。随着优质原材料及燃料的逐渐匮乏，低品位原料(如高硫石灰石)、燃料(如高硫煤)逐渐应用于熟料生产。含硫量较高的原、燃料应用于熟料生产后，除SO 2排放量增加带来的环境污染，还影响熟料的生产工艺：首先，原、燃料中的部分硫以硫酸盐形式进入熟料，在超过一定量后易对熟料质量产生不利影响；其次，SO 2在新型干法窑系统中的循环、富集(主要集中于预热器下段和回转窑高温带之间)会造成如回转窑结皮、结圈甚至预热器堵塞等一系列问题，进而影响正常窑生产。发明专利201510946574.2公开了一种水泥窑旁路放风联合分级燃烧窑尾烟气处理装置及工艺方法，以改善过量钾、钠、氯及硫在窑内循环所带来的一系列问题。现有技术采用旁路放风、减少硫挥发及控制硫的凝结位置等技术措施，虽然一定程度上改善了新型干法窑系统中SO 2循环，但需改造现有设备，同时存在热能损失大等问题。发明专利201510033679.9公开了一种气相沉积合成硫铝酸钙改性硅酸盐水泥熟料的方法，该方法利用气相SO 2与新烧成熟料中的CaO生成高活性CaSO 4，新生CaSO 4与熟料中的C 3A固相反应形成硫铝酸钙。这为回转窑中硫循环的改善提供了借鉴。
因此，对于目前采用高含硫量原、燃料的水泥生产企业，如何在兼顾熟料吨煤耗成本、熟料品质和大气污染物SO 2排放控制的前提下，改善SO 2循环对熟料烧成影响，并稳定烧成含硫相高性能水泥熟料，是目前急需解决的技术难题之一。
发明内容
本发明所要解决的主要技术问题，是提供一种含硫矿物改性硅酸盐水泥熟料的生产方法，尤其涉及废弃混凝土中的水泥硬化砂浆在该水泥熟料生产中的 应用。也提供一种改善硫酸盐在回转窑高温段分解而导致的硫循环的方法。在窑头位置喷入的水泥硬化砂浆微粉颗粒，遇高温烟气后迅速脱水并形成高活性、高比表面积的轻质颗粒(含活性CaO等)，在由二次风带入后高温段后，其与硫酸盐分解逸出的部分SO 2反应并固硫沉降。
为解决上述技术问题，本发明的基本思路是：在基本不改变新型干法窑中硅酸盐水泥熟料烧成工况的前提下，从回转窑的窑头位置喷入一定量的改性水泥硬化砂浆微粉；改性水泥砂浆微粉遇高温烟气迅速脱水并形成高活性、高比表面积的轻质颗粒(含活性CaO、脱水C-S-H等)，由二次风带入后高温段并与硫酸盐分解逸出的部分SO 2反应，新生CaSO 4并沉降入后高温带或前冷却带位置的已烧成的硅酸盐水泥熟料中。改性水泥硬化砂浆微粉中未反应组分在沉降过程中受热分解，如C-S-H脱水、分解为C 2S，含硫水化产物Aft/AFm脱水、分解为CaSO 4等。
具有较高反应活性的新生CaSO 4(包括活性CaO捕捉SO 2气体形成的CaSO 4和水化产物Aft/AFm脱水分解形成的CaSO 4)能与熟料中的C 2S(尤其是改性微粉中C-S-H脱水、分解形成的新生C 2S)及C 3A/C 4AF在后高温段、前冷却带经二次固相反应形成硫硅酸钙(2C 2S.CaSO 4)和硫铝酸钙
Figure PCTCN2019080472-appb-000001
并稳定存在，最终获得
Figure PCTCN2019080472-appb-000002
多矿相复合的硅酸盐水泥熟料。
为了实现上述目的，本发明的技术方案为：
一种含硫矿物改性硅酸盐水泥熟料的生产方法，其特征在于，将改性水泥硬化砂浆微粉，从新型干法回转窑的窑头位置利用喷煤管向窑内加入；该微粉遇高温烟气脱水并形成高活性、高比表面积的轻质颗粒(含活性CaO、脱水C-S-H等)，通过与高温段的硫酸盐分解产生的SO 2气固反应形成新生CaSO 4，沉降到熟料中；并在后高温段、前冷却带经二次固相反应形成硫硅酸钙和硫铝酸钙，最终获得一种含硫矿物改性的硅酸盐水泥熟料；其中所述的改性水泥硬化砂浆微粉由以下方法制备得到：将废弃混凝土破碎、分离粗骨料后得到的硬化水泥砂浆，然后在粉磨过程中加入液体助剂以对粉体进行表面改性，最后选粉分离硅质细集料(一般为石英砂)后获得以的活性氢氧化钙(CH)、水化硅酸钙(C-S-H)等为主要成分的改性水泥硬化砂浆微粉。
上述的含硫矿物为硫硅酸钙(2C 2S.CaSO 4)和硫铝酸钙
Figure PCTCN2019080472-appb-000003
含硫矿物 改性硅酸盐水泥熟料是指
Figure PCTCN2019080472-appb-000004
多矿相复合的硅酸盐水泥熟料。
上述的改性水泥硬化砂浆微粉为有机改性的以活性氢氧化钙(CH)、水化硅酸钙(C-S-H)及少量含铝水化产物(Aft及AFm)为主要成分的混合粉体。
优选所述的粉磨所用粉磨设备为球磨机或立磨。
优选所述的液体助剂为多元醇的水溶液，水溶液中溶质的质量浓度范围为30％～60％。
优选所述的多元醇为乙二醇(EG)、二乙二醇(DG)、1,2-丙二醇(MPD)或丙三醇中任意一种或多种的水溶液。
优选所述的液体助剂的掺入量为硬化水泥砂浆质量的0.03～0.08％。
优选所述的改性水泥硬化砂浆微粉的80um筛余量为1.0～3.0％。
优选改性水泥硬化砂浆微粉向窑内加入质量为生料喂料质量的2～10％。
从上述技术方案可以看出，本发明提供一种含硫矿物改性硅酸盐水泥熟料的生产方法，尤其涉及废弃混凝土中的水泥硬化砂浆在该水泥熟料生产中的应用。包括：首先将废弃混凝土破碎、分离粗骨料后得到的硬化水泥砂浆，经粉磨、选粉，粉磨过程中加入液体助剂对粉体进行表面化学改性，并通过选粉设备分离硅质细集料(石英砂)，进而获得改性水泥硬化砂浆微粉；将所述改性水泥硬化砂浆微粉从新型干法回转窑的窑头位置利用喷煤管加入窑内，最终获得含硫矿物改性硅酸盐水泥熟料。
回转窑的窑头位置喷入的改性水泥硬化砂浆微粉在遇到窑内高温烟气后，微粉中的氢氧化钙(CH)、水化硅酸钙(C-S-H)迅速脱水形成含新生的活性CaO的轻质脱水微粉。该脱水微粉具有高比表面积、多孔、轻质等特点，易被二次风带入回转窑的后高温段。微粉中新生的活性CaO与熟料中的硫酸盐分解逸出的部分SO 2反应，生成CaSO 4并沉降入熟料中(未完全反应的活性CaO由于未经高温烧结，为非致密性CaO，不仅不影响水泥安定性，反而可提高初始碱度并促进水泥水化)；而这一区间段(后高温带或前冷却带位置)的硅酸盐水泥熟料已完成烧成。微粉中的其它组分逐渐受热分解，如含量最大的水化硅酸钙C-S-H脱水、分解为活性C 2S，含硫水化产物Aft/AFm则脱水、分解为CaSO 4等。通过上述两种途径新生的CaSO 4(包括活性CaO捕捉SO 2气体形成的CaSO 4和水化产物 Aft/AFm脱水分解形成的CaSO 4)具有较高的固相反应活性，能与熟料中的大量C 2S(尤其是微粉中C-S-H脱水、分解形成的新生的高活性C 2S)及C 3A/C 4AF在后高温段、前冷却带这一区间经二次固相反应形成硫硅酸钙和硫铝酸钙并最终随熟料出窑，获得
Figure PCTCN2019080472-appb-000005
多矿相复合的硅酸盐水泥熟料。
硫硅酸钙(2C 2S.CaSO 4)是含硫量较高的硅酸盐水泥熟料和硫铝酸盐水泥熟料煅烧过程中的一种中间矿物：当煅烧温度在900～1200℃范围时，贝利特和硬石膏反应形成硫硅酸钙并稳定存在；当煅烧温度超过1200℃时，硫硅酸钙会再次分解为贝利特和硬石膏。N.Sherman等提出了一种硫铝酸盐-硫硅酸盐熟料的制备方法，并研究了以这种熟料制备的高强度水泥的性质；在1200℃的煅烧温度下，熟料体系中的β-C 2S和CaSO 4更趋向以硫硅酸钙(2C 2S.CaSO 4)形式存在；所制备的该种熟料的3d/28d净浆强度为35～50Mpa和58～76Mpa，在与粉煤灰等复合后，其3d净浆抗压强度为50-80Mpa,而28d则达到103Mpa；其体积稳定性及抗碳化性能均与硅酸盐水泥类似(N.Sherman,J.Beretka,L.Santoro and G.L.Valenti，Long term behavior of hydraulic binders based on calcimu sulfoaluminate and calcium sulfosilicate.Cement and Concrete Research,1995,25(1):113-126)。
WO2013023728 A3公开了一种含有硫硅酸盐的硫铝酸盐水泥熟料及其制备方法，以及这种熟料作为硫铝酸盐水泥的添加剂的应用。申请号为201711222374.8的中国发明专利公开了一种利用硫硅酸钙矿物改性硫铝酸盐水泥的方法，提高了硫铝酸盐的后期强度并改善了后期倒缩。本发明的技术方案中，硬化水泥砂浆微粉中的水化硅酸钙在进入窑内后经(C-S-H)脱水、分解产生的C 2S，其反应活性高于经高温烧结的原熟料中的C 2S(杨南如,钟白茜.活性β-C 2S的研究.硅酸盐学报,1982,10(2):161-166)；因此利用新生的高反应活性的CaSO 4与熟料中的大量C 2S，尤其是微粉中水化硅酸钙(C-S-H)脱水、分解形成的新生的高活性C 2S，通过固相反应形成硫硅酸钙(2C 2S.CaSO 4)；这一区间段(后高温带或前冷却带位置)的温度有利于硫硅酸钙(2C 2S.CaSO 4)的形成及稳定存在。而后高温段、前冷却带这一区间段也同样有利于原熟料中存在的C 3A/C 4AF矿物与新生的CaSO 4固相反应形成硫铝酸钙
Figure PCTCN2019080472-appb-000006
矿物。
本发明的技术方案中，硬化水泥砂浆经预粉磨、选粉，并在粉磨过程中加入 液体助剂对粉体进行表面化学改性，通过选粉设备分离硅质细集料(石英砂)，进而获得改性水泥硬化砂浆微粉。粉磨的目的是为了提高微粉能够参与化学反应的比表面积，以加快其在进入窑内后各项化学反应如脱水、固硫及固相反应的速率；粉磨过程中加入以多元醇为主要成分的液体助剂对粉体进行表面化学改性；一方面，该液体助剂以多羟基的多元醇为主要成分，在粉磨过程中加入有助磨与分散的作用，提高了粉磨效率并优化颗粒分布；此外，该液体助剂在粉体表面的均匀分布，改变了粉体的气-固两相表面性能，并显著提高了其喷入窑内烟气中的分散程度，有利于热交换及与烟气中SO 2的气固反应的进行。
水泥硬化砂浆中的石英砂由于结晶度高，影响熟料的易磨性。在粉磨过程中利用选粉机的风力分选原理将石英砂分离用作再生细集料(Recycled Fine Aggregate,RFA)，避免了结晶度高的石英砂对熟料易磨性及不溶物指标的影响。
有益效果：
与现有技术相比，本发明工艺简单、流程短、易推广，在基本不改变新型干法窑中硅酸盐水泥熟料烧成工况的前提下，通过在窑头喷入改性水泥硬化砂浆微粉，一方面通过气固反应过程，实现了回转窑中高温带的硫酸盐分解逸出的部分SO 2的固化及硫循环改善；另外一方面，分别利用气固反应及含硫水化产物脱水分解所生成的新生CaSO 4与C-S-H分解所生成的活性C 2S，二次固相反应生成硫硅酸钙和硫铝酸钙矿物，实现
Figure PCTCN2019080472-appb-000007
多相复合熟料体系的烧成。
本发明的另外一个有益效果是，在基本不增加窑系统负荷及能耗的情况下，实现了熟料产量的增加，降低了吨熟料烧成能耗。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部实施例；根据下述实施例，可以更好地理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。基于本发明中的实施例，本领域普通技术人员在没做出任何创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1：
实施例1中使用的硬化水泥砂浆取自某废弃混凝土生产再生粗骨料(RCA)工厂A，为分离RCA后的细颗粒部分(0.2mm筛余<25％,含水量1.5％)，主要为硬化水泥砂浆，含少量粘土杂质。用球磨机粉磨该硬化水泥砂浆并选粉分离硅质石英砂，获得改性水泥硬化砂浆微粉(80um筛余量2.1％，含水量1.4％)，入库均化备用。粉磨过程中加入0.05％的液体助剂，为质量浓度为45％的乙二醇(EG)水溶液。
西南地区某2500t/d新型干法水泥熟料生产线(回转窑规格为Φ4m×60m，斜度4％，MFC型分解炉和五级悬浮预热器，第三代TC型充气梁篦冷机)，该厂所用烟煤含硫量较高(S t.ad＝3.8％，艾士卡法)，窑内结圈严重并影响烧成。将本实施例的改性水泥硬化砂浆微粉，按照入窑生料量的5.5％在窑头位置通过喷煤管加入窑内，生产了本发明的含硫矿物改性硅酸盐水泥熟料，窑产量约增加约3.8％。
对应用本实施例技术前后所生产熟料的平均样，按照《GB/T21372-2008硅酸盐水泥熟料》《GB/T17671 1999水泥胶砂强度检验方法(ISO法)》进行了性能检测，如表1。
表1采用实施例1技术前后所生产水泥熟料的性能对比
Figure PCTCN2019080472-appb-000008
比较可知，应用本发明实施例技术得到的水泥熟料的早期强度及后期强度均对比应用前熟料强度明显改善；化学指标中游离钙f-CaO略有增加，主要是改性水泥硬化砂浆微粉中未完成反应的CaO造成的，但是对安定性无影响(合格)；不溶物含量略有增加，可能和夹入的少量石英砂有关；熟料中的SO 3含量增加明细，主要是固硫及改性水泥硬化砂浆微粉带入的石膏有关；凝结时间(初、终凝)略有缩短。从上述情况来看，采用本发明的实施例1后，熟料性能得到明显改善，f-CaO、不溶物及SO3等指标虽然有明细增加，但未影响熟料安定性及强度性能。
实施例2：
实施例2中使用的硬化水泥砂浆取自某废弃混凝土生产再生粗骨料(RCA)工厂B，为分离RCA后的块状及粉状的硬化水泥砂浆混合物(0.2mm筛余<35％,含水量2.3％)，碎砖瓦、瓷砖等含量约3.2％。将该块状硬化水泥砂浆预破碎，用立磨烘干、粉磨该硬化水泥砂浆并选粉分离硅质石英砂，获得改性水泥硬化砂浆微粉(80um筛余量2.8％，含水量0.8％)，入库均化备用。粉磨过程中加入0.08％的液体助剂，为质量浓度为32％的二乙二醇(EG)和丙三醇的混合水溶液，其中二乙二醇和丙三醇的质量比为12:20。
陕西地区某5000t/d新型干法水泥熟料生产线(回转窑规格为Φ4.8m×72m，斜度4％，TDF型分解炉(Φ7.4m×26.6m)和五级悬浮预热器，第三代TC型充气梁型推动篦式冷却机)，该厂所用烟煤含硫量较高(S t.ad＝3.2％，艾士卡法)，窑内结圈明显。将本实施例的改性水泥硬化砂浆微粉，按照入窑生料量的2.5％在窑头位置通过喷煤管加入窑内，生产了本发明的含硫矿物改性硅酸盐水泥熟料，窑产量约增加约2％。
对应用本实施例技术前后所生产熟料的平均样，按照《GB/T21372-2008硅酸盐水泥熟料》、《GB/T17671 1999水泥胶砂强度检验方法(ISO法)》进行了性能检测，如表2。
表2采用实施例2技术前后所生产水泥熟料的性能对比
Figure PCTCN2019080472-appb-000009
比较可知，应用本发明实施例2技术得到的水泥熟料的早期强度及后期强度均对比应用前熟料强度明显改善；不溶物含量略有增加，可能和夹入的少量石英砂有关；熟料中SO 3含量的增加主要是固硫及改性水泥硬化砂浆微粉带入的石膏有关；凝结时间(初、终凝)略有缩短。从上述情况来看，采用本发明的实施例2后，熟料性能得到明显改善，f-CaO、不溶物及SO 3等指标虽略有增加，但未影响熟料安定性及强度性能。
实施例3：
实施例3中使用的硬化水泥砂浆取自某废弃混凝土生产再生粗骨料(RCA)工厂C，为分离RCA后的粉状的硬化水泥砂浆(0.2mm筛余<18％,含水量2.8％)，含少量碎砖瓦、瓷砖、粘土等杂质(<1％)。将粉状硬化水泥砂浆预烘干，利用球磨剂粉磨该硬化水泥砂浆并选粉分离硅质石英砂，获得改性水泥硬化砂浆微粉(80um筛余量1.1％，含水量1.0％)，入库均化备用。粉磨过程中加入0.03％的液体助剂，为质量浓度为60％的丙二醇、二乙二醇和丙三醇的混合水溶液，其中丙二醇、二乙二醇和丙三醇的质量比为1:1:1。
安徽某5000t/d新型干法水泥熟料生产线(回转窑规格为Φ5.2m×61m，TDF型分解炉和五级悬浮预热器，第三代TC型可控气流篦式冷却机)，该厂所用烟煤含硫量高(S t.ad＝4.8％，艾士卡法)，窑内结圈严重影响生产。将本实施例的改性水泥硬化砂浆微粉，按照入窑生料量的8.5％在窑头位置通过喷煤管加入窑内，生产了本发明的含硫矿物改性硅酸盐水泥熟料，窑产量约增加约6.6％。
对应用本实施例技术前后所生产熟料的平均样，按照《GB/T21372-2008硅酸盐水泥熟料》、《GB/T17671 1999水泥胶砂强度检验方法(ISO法)》进行了性能检测，如表3。
表3采用实施例3技术前后所生产水泥熟料的性能对比
Figure PCTCN2019080472-appb-000010
比较可知，应用本发明实施例技术得到的水泥熟料的早期强度及后期强度均对比应用前熟料强度明显改善，其中3d抗压强度增加1.3Mpa，28d抗压强度增加3.5Mpa；化学指标中游离钙f-CaO增加明细，达到1.4～1.8％(上限已超过GB/T21372-2008指标<1.5％)，这主要是改性水泥硬化砂浆微粉带入的氢氧化钙分解为活性CaO所造成的，由于其为未经高温烧结的非致密CaO，不仅不影响水泥安定性，反而可提高初始碱度并促进水泥水化；不溶物含量略有增加，可能和夹入的少量石英砂有关；熟料中的SO 3含量增加明显，主要是固硫及改性水泥硬化砂浆微粉带入的石膏有关；凝结时间(初、终凝)略有缩短。从上述情况来看，采用本发明的实施例3后，熟料性能得到改善，f-CaO、不溶物及SO 3等指 标虽有明细增加，但未影响熟料安定性及强度性能。
对应用本实施例技术前后所生产熟料的平均样，按照该厂P.O42.5的水泥物料配比进行小磨实验，并按照按照《GB 175-2007通用硅酸盐水泥》进行相关性能检测，如表4。
表4采用实施例3熟料所制备P.O 42.5水泥的性能对比(小磨实验)
Figure PCTCN2019080472-appb-000011
比较可知，应用本发明实施例3的水泥熟料采用试验磨制备的P.O 42.5水泥，其筛余量略有降低，标准稠度需水量则增加了0.4％；3d、28d强度均明显提高，且强度增进尤其是28d抗压强度增进明显高于熟料(如表3)；说明本发明实施例制备的熟料能有效激发混合材(粉煤灰)活性，加速其水化进程。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般远离可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (8)

  1. 一种含硫矿物改性硅酸盐水泥熟料的生产方法，其特征在于将改性水泥硬化砂浆微粉，从新型干法回转窑的窑头位置利用喷煤管向窑内加入，最终获得一种含硫矿物改性的硅酸盐水泥熟料；其中所述的改性水泥硬化砂浆微粉由以下方法制备得到：将废弃混凝土破碎、分离粗骨料后得到的硬化水泥砂浆，然后在粉磨硬化水泥砂浆过程中加入液体助剂对粉体进行表面改性，选粉后获得改性水泥硬化砂浆微粉。
  2. 根据权利要求1所述的生产方法，其特征在于所述的含硫矿物为硫硅酸钙(2C 2S.CaSO 4)和硫铝酸钙
    Figure PCTCN2019080472-appb-100001
    含硫矿物改性硅酸盐水泥熟料是指
    Figure PCTCN2019080472-appb-100002
    多矿相复合的硅酸盐水泥熟料。
  3. 根据权利要求1所述的生产方法，其特征在于所述的粉磨所用粉磨设备为球磨机或立磨。
  4. 根据权利要求1所述的生产方法，其特征在于所述的液体助剂为多元醇的水溶液，水溶液中溶质的质量浓度范围为30％～60％。
  5. 根据权利要求4所述的生产方法，其特征在于所述的多元醇为乙二醇、二乙二醇、1,2-丙二醇或丙三醇中任意一种或多种的水溶液。
  6. 根据权利要求1所述的生产方法，其特征在于所述的液体助剂的掺入量为硬化水泥砂浆质量的0.03～0.08％。
  7. 根据权利要求1所述的生产方法，其特征在于所述的改性水泥硬化砂浆微粉的80um筛余量为1.0～3.0％。
  8. 根据权利要求1所述的生产方法，其特征在于改性水泥硬化砂浆微粉向窑内加入质量为生料喂料质量的2～10％。
PCT/CN2019/080472 2018-07-19 2019-03-29 一种含硫矿物改性硅酸盐水泥熟料的生产方法 WO2020015382A1 (zh)

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EP1171398A1 (en) * 1999-04-16 2002-01-16 KUNBARGI, Hassan Rapid hardening, ultra-high early strength portland-type cement compositions, novel clinkers and methods for their manufacture
CN1990410A (zh) * 2005-12-27 2007-07-04 尹小林 废弃混凝土活化再生水泥技术
CN103396020A (zh) * 2013-08-13 2013-11-20 尹无忌 一种废弃混凝土作为水泥生产中的活性掺合材的方法
CN108911537A (zh) * 2018-07-19 2018-11-30 南京工业大学 一种含硫矿物改性硅酸盐水泥熟料的生产方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1171398A1 (en) * 1999-04-16 2002-01-16 KUNBARGI, Hassan Rapid hardening, ultra-high early strength portland-type cement compositions, novel clinkers and methods for their manufacture
CN1990410A (zh) * 2005-12-27 2007-07-04 尹小林 废弃混凝土活化再生水泥技术
CN103396020A (zh) * 2013-08-13 2013-11-20 尹无忌 一种废弃混凝土作为水泥生产中的活性掺合材的方法
CN108911537A (zh) * 2018-07-19 2018-11-30 南京工业大学 一种含硫矿物改性硅酸盐水泥熟料的生产方法

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