TWI634095B - Environmentally friendly portland cement, preparation methods and applications thereof - Google Patents

Abstract

This application relates to environmentally friendly Portland raw meal and clinker prepared using chemical mechanical polishing (CMP) waste and a method for preparing the same. This application also relates to the application of environmentally friendly Portland cement clinker, for example as a concrete raw material.

Description

Environmentally friendly Portland cement, its preparation method and its application

This application relates to environmentally friendly Portland raw meal and clinker prepared using chemical mechanical polishing (CMP) waste and a method for preparing the same. This application also relates to the application of environmentally friendly Portland cement clinker, for example as a concrete raw material.

Cement is a general term for cementitious materials commonly found in building materials and is one of the most important building materials available today. Cement can be classified into hydraulic cement and non-hydraulic cement according to the difference in cementation properties. Cement is also classified into silicate cement, aluminate cement, sulphoaluminate cement, etc. according to the mineral component. Among them, silicate cement is also known as Portland cement. It has a wide application range and can use different types of Portland cement according to requirements.

Portland cement contains main components such as calcium oxide, cerium oxide, aluminum oxide, iron oxide, etc., and uses components of different content ratios for the purpose of use and properties. These main components may, for example, be provided by ore raw materials such as limestone, clay, antimony ore and iron slag, respectively. However, mining ore raw materials have a great burden and impact on the environment, and the mineral resources content is not unlimited. Therefore, in recent years, it has begun to look for raw materials to replace ore raw materials to reduce the environmental and economic costs of preparing cement.

The waste components of some semiconductor industries are similar to the main components of Portland cement, and it has been reported in the literature that the waste of the semiconductor industry can be used as a substitute raw material for cement raw materials. According to this, it is possible to use waste generated by the semiconductor industry as a substitute raw material. For example, the waste liquid generated by the chemical mechanical polishing (CMP) method used in the semiconductor industry and the solid waste generated by the treated waste liquid contain a part of the main component of the cement.

The chemical mechanical polishing (CMP) method is currently a process for mainly flattening the surface of a wafer, and includes flattening using a polishing pad and a polishing liquid. In the CMP slurry, a large amount of nano-sized cerium oxide (SiO ₂ ) particles are usually contained as abrasive granules, and after the polishing liquid is used for grinding, the abrasive granules are still suspended in the generated wastewater. In order to reduce the impact of waste emissions on the environment and comply with regulatory emission standards, the wastewater generated by the CMP process must be discharged through a certain process. In general, solid sludge consisting of abrasive granules, floes, and treatment additives (collectively referred to herein as "CMP sludge") is produced after treatment. The CMP sludge produced is usually treated by landfill. However, if extremely fine-sized waste particles are precipitated due to environmental stress (such as weathering or rain), it may flow into the groundwater body to cause secondary pollution.

In order to avoid the above-mentioned secondary pollution caused by the burying method, CMP sludge can be tried as a substitute for some raw materials in the cement clinker for manufacturing concrete, and the environmental and economic cost of manufacturing cement can be reduced. However, due to the limitation of the amount of cement clinker replaced by CMP sludge, the benefits of this approach to reducing environmental and economic costs are still limited. If the CMP sludge can be directly used as a raw material for cement raw materials, it will not only eliminate the problems caused by burying CMP sludge, but also reduce the demand for mining. However, there are still many technical problems to be overcome in practice.

Accordingly, the present application relates to an environmentally friendly Portland cement raw meal prepared using chemical mechanical polishing (CMP) sludge, which comprises a calcareous material, a clay material, a ferrous material, and a chemical mechanical polishing (CMP) sludge, wherein The CMP sludge contains less than 40% by weight of its own fluorine, and wherein the cement raw meal contains at least 0.024% by weight of rhodium. The environmentally friendly Portland cement raw material can be, for example, in accordance with the wave Raw materials for the raw material composition and properties of Portland Type I, Type IA, Type II, Type IIA, Type II (MH), Type II (MH) Type A, Type III, Type IIIA, Type IV and Type V cement.

This application also relates to environmentally friendly Portland cement clinker, characterized in that the clinker contains at least 0.024% by weight of rhodium.

The present application also relates to a method for preparing environmentally-friendly Portland cement clinker by preparing the aforementioned Portland cement raw meal by rotary kiln sintering.

This application also relates to the application of environmentally friendly Portland cement clinker, for example as a concrete raw material.

Figure 1 shows the setting time of Portland cement clinker made from traditional Portland cement raw meal and using CMP sludge as part of the environmentally friendly Portland cement raw meal.

Environmentally friendly Portland cement raw meal

The environmentally friendly Portland cement raw meal of the present application comprises a calcareous material, a clay material, a ferrous material, and a chemical mechanical polishing (CMP) sludge. Further explanation of each component is given below:

A. Calcareous material

The calcareous material in the environmentally friendly Portland cement raw meal of the present application accounts for about 72.0 to 96.0% by weight, preferably 78.0 to 93.0% by weight, more preferably 85.0 to 90.0% by weight, based on the total weight of the raw meal. The main component of the calcareous material is a substance capable of providing calcium oxide, such as calcium carbonate, calcium hydroxide, etc., which may provide a calcium oxide content of at least about 43% by weight or more, preferably 48% by weight or more. More preferably, it is 53% by weight or more.

Examples of calcareous materials are, for example, but not limited to, natural limestone, marble, chalk minerals, steelmaking slag, calcium hydroxide, and the like.

Preferably, the calcareous material may also comprise other essential chemical constituents of Portland cement, such as cerium oxide, aluminum oxide and/or iron oxide. Examples may be marl soil or the like.

B. Clay material

The clay material in the environmentally friendly Portland cement raw meal of the present application accounts for about 1.6 to 11.0% by weight, preferably 3.0 to 9.3 % by weight, more preferably 4.7 to 7.6% by weight, based on the total weight of the raw meal. The main component of the clay material is a material which can provide alumina, such as a base containing aluminum citrate, an alkaline earth and a chemical conversion thereof. The materials may provide an alumina content of at least about 10.0% by weight, preferably 20.0% by weight or more, more preferably 40.0% by weight or more.

Examples of clayaceous materials are, for example, but not limited to, natural clay minerals, waste soils produced by engineering excavation, kaolin, fly ash from power plant operations, minerals containing feldspar and/or mica, and the like.

C. Iron material

The iron material in the environmentally friendly Portland cement raw meal of the present application accounts for about 1.7 to 2.4% by weight, preferably 1.9 to 2.3% by weight, more preferably 2.0 to 2.2% by weight, based on the total weight of the raw meal. The main component of the clay material is a substance that can provide iron oxide, such as iron hydroxide, iron sulfide, and the like. These materials may provide an iron oxide content of at least about 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more.

Examples of ferrous materials are, for example, but not limited to, natural iron ore, steel slag, and the like.

D. Chemical polishing (CMP) sludge

In general, traditional Portland cement, in addition to the aforementioned calcareous materials, clay materials and iron materials, must also contain antimony ore materials, mainly used to provide antimony oxide components. Examples of antimony ore materials are natural antimony ore, steelmaking grit, glass, ready mixed concrete waste mud, and the like. However, if the tantalum ore material is the higher unit price of Portland cement raw materials, if the niobium ore can be replaced by a lower cost raw material, the production and environmental costs will be greatly reduced.

The chemical mechanical polishing (CMP) method is currently used in the semiconductor industry for wafer surface planarization, which uses abrasive and corrosive polishing liquids and polishing pads to polish the surface of the wafer to obtain a flat surface. The surface to be polished may be an (oxidized) tantalum layer or a metal layer. The polishing liquid of the former is usually composed of cerium oxide, aluminum oxide and cerium oxide; the polishing liquid used for grinding the latter is composed of the nature of the metal to be ground. It is different. The waste liquid produced by grinding the surface of the wafer contains substances removed from the surface in addition to the components (abrasive particles, carriers, additives, etc.) contained in the polishing liquid itself. After the waste liquid is treated (for example, adding a flocculating agent, electrolytic coagulation method), the waste water is separated from the solid matter, and the solid substance is CMP sludge.

The main components of the CMP sludge derived from the oxidized (oxidized) ruthenium layer are ruthenium dioxide and ruthenium oxide, and may further comprise calcium, iron, aluminum, sodium, copper, tungsten, magnesium, sulfur, and various elements formed by the aforementioned elements together with oxygen. a compound, or any combination of the foregoing. Applicants have surprisingly found that chemical polishing (CMP) sludge derived from grinding (oxidizing) ruthenium layer can be used as an ingredient in environmentally friendly Portland cement raw meal instead of bismuth ore material, and successfully prepared and Traditional Portland cement has environmentally friendly and environmentally friendly Portland cement. Compared with the traditional Portland cement using antimony ore materials, the alkali content of the antimony ore is usually very high (usually not less than 2% by weight of itself), and the chemical polishing polishing derived from the grinding (oxidation) layer The (CMP) sludge itself has a very low alkali content (preferably not higher than 0.9% by weight of itself), that is, the contribution of the CMP sludge to the alkali content of the cement clinker after sintering is only 45 of that of the general antimony ore. % or lower), it is expected that the cement raw material obtained by using CMP sludge as a material for replacing the antimony ore has a low alkali content; and after being fired into Portland cement at a high temperature, a cement having a low alkali content can be obtained. . The reduction of the alkali content improves the workability of the cement, the compatibility of the water reducer, and the problem of swelling of the aggregate caused by avoiding the alkali, thereby improving the performance of the Portland cement.

In addition, CMP sludge usually contains too much CaF ₂ component, and the fluorine contained in it will greatly prolong the cement setting time, fail to meet the properties of cement, and may also degrade the performance of cement (for example, reduce the pressure resistance); In the process, it is easy to cause the equipment to be corroded. The CMP sludge derived from the ground (oxidized) ruthenium layer used in the application should have a fluorine content of not more than 40% by weight of itself, preferably not more than 20% by weight of itself, to avoid causing cement condensation. Time is greatly extended, and the compressive strength is reduced.

The CMP sludge in the environmentally friendly Portland cement raw meal of the present application accounts for about 0.6 to 8.1% by weight, preferably 1.7 to 6.8% by weight, more preferably 2.8 to 5.4% by weight, based on the total weight of the raw meal. The CMP sludge may provide a cerium oxide content of at least about 60% by weight or more, preferably 65% by weight or more, more preferably 70% by weight or more.

The water content of the CMP sludge is not particularly limited. In order to facilitate the preparation of the clinker, the water content is preferably not more than 70% by weight of itself, more preferably not more than 60% by weight of itself, and most preferably not more than 50% by weight of itself.

Preferably, the CMP sludge has an alkali content of not more than 2% by weight, more preferably not more than 1.4% by weight, still more preferably not more than 0.9% by weight.

The alkali content described herein is calculated by the CNS 61 standard (0.658*K ₂ O+Na ₂ O).

E. The remaining components

The environmentally friendly Portland cement of the present application may also contain mineral or elemental impurities such as magnesium, sulfur, potassium, sodium, phosphorus, titanium, strontium, manganese, chromium, chlorine, etc. or the elements other than chlorine and oxygen. Various types of compounds. However, the content of such impurities is preferably not more than 5% by weight of the green Portland cement raw meal, more preferably not more than 4% by weight.

Alkali content

The alkali content in the environmentally-friendly Portland cement raw meal of the present application is preferably 0.5% or less, more preferably 0.3% or less.

Environmentally friendly Portland cement raw material manufacturing method

According to different types of environmentally friendly Portland cement clinker to be manufactured (for example, according to conventional standards, such as ASTM C150, EN 197, etc.), and the necessary composition ratio of the clinker, the content of each of the foregoing raw materials is adjusted to Prepare environmentally friendly Portland cement raw meal that meets a specific ratio of ingredients.

For example, according to the required combination of components, the feed ratio of the raw materials is controlled, uniformly mixed, and then ground into a powder to obtain an environmentally friendly Portland cement raw meal.

In a preferred embodiment, a feed system capable of feeding a high water content CMP sludge is introduced into a cement raw meal production system to prepare an environmentally friendly Portland cement raw meal. In another preferred embodiment, the CMP sludge is treated prior to drying to a water content of less than 30% (preferably less than 7%) and then introduced into a cement raw meal production system to prepare an environmentally friendly Portland cement raw meal. . The advantage of using CMP sludge that has been treated prior to drying is that it can be fed and ground using existing equipment from cement processes. The drying method may include dehydration, such as vacuum filtration dehydration, pressure filtration dehydration, and centrifugal dehydration, for example, using a belt filter press dewatering machine, a plate and frame filter press dewatering machine, a screw extrusion dewatering system, or a centrifugal dewatering machine for dehydration; Heating or airflow dewatering, for example using a dehumidification drying system, a heat transfer drying system, a continuous turbine drying system, and the like.

Environmentally friendly Portland cement clinker and preparation method thereof

As mentioned above, the environmentally friendly Portland cement raw meal can be further sintered to prepare environmentally friendly Portland cement clinker. The components required for Portland I to V cement clinker can be, for example but not limited to, the following Table 1:

The weight ratios of the foregoing components are for reference only, and those skilled in the art can adjust the raw meal ratio to meet the selected specifications according to requirements and various specifications.

After preheating and calcining the environmentally-friendly Portland cement raw material, it is sent to the rotary kiln for clinker sintering, and the environmentally-friendly Portland cement clinker can be obtained through subsequent processing steps (such as cooling, grinding, etc.). Do not want to be bound by theory, by having two oxidation states cerium (Ce (III) and Ce (IV)), which may assist in the further oxidation of CO in the exhaust gas and the NO _x in the sintering process to reduce the content of NO _x and CO The reaction formula of cerium oxide with CO may be as follows: 4CeO ₂ +2CO → 2Ce ₂ O ₃ +2CO ₂

The environmentally-friendly Portland cement clinker prepared, in addition to determining the proportion of essential components, also comprises at least about 0.024% by weight, preferably at least 0.05% by weight, more preferably at least 0.10% by weight, based on the total weight of the cement clinker; The cerium content is preferably at most 0.30% by weight, more preferably at most 0.25% by weight.

The alkali content in the environmentally-friendly Portland cement clinker of the present application is preferably 0.6% or less, more preferably 0.4% or less; and the fluorine content is preferably less than 0.04% by weight or less, more preferably less than 0.03% by weight or less.

Concrete

Concrete generally contains components such as cement, water, aggregates and materials. Therefore, the aforementioned environmental protection can be Portland cement clinker is formed by adding appropriate additives and grinding to form a concrete component of concrete and further mixing with other ingredients to form concrete.

Different additives can be added depending on the purpose of use. The most common additive is gypsum, which is added in an amount of about 4 parts by weight or more, preferably 5 parts by weight or more, based on 100 parts by weight of the environmentally-friendly Portland cement clinker; usually not more than 8 parts by weight, preferably not higher than 6 parts by weight so that the SO ₃ content is not more than 3.5%, preferably not more than 3.0%. Examples of gypsum are natural gypsum, desulfurization gypsum in thermal power plants, flue desulfurization gypsum, waste gypsum, etc., or calcium sulfate dihydrate, calcium sulfate hemihydrate or mixtures thereof.

The remaining examples of the additive include pure limestone, water quenched blast furnace grate, fly ash, etc., and the additive content is preferably 5 parts by weight or less, more preferably 4 parts by weight or less, based on 100 parts by weight of the Portland cement clinker.

The aggregate is mainly used as a filler in concrete. It is usually cheaper and can be used to increase the volume of the finished product, as well as to resist abrasion, moisture penetration and weathering, and to reduce the volume change of concrete due to hard solidification. Examples of the aggregates are artificial aggregates made of natural river sand or mountain ore, including calcareous materials, quartz materials, etc., preferably quartz materials. For example, the aggregate may be derived from granite, andesite, basalt, hard sandstone, hard rock, and the like.

The role of the admixture is to reduce the material or construction cost, improve the workability of the concrete, control the concrete bonding time, increase the concrete strength, improve the resistance, etc., so that the concrete can exhibit special engineering properties. The admixture comprises a chemical admixture and a mineral admixture. Examples of the chemical admixture are a quick setting agent, a retarder, a gas carrier, a water reducing agent, a strong plasticizer, a corrosion inhibitor, a foaming agent, a getter, and a pump. Etc. Examples of mineral admixtures are volcanic ash, shale clay, diatomaceous earth, rice husk ash, ash ash, and the like.

The nature of environmentally friendly Portland cement

In addition to the raw material ratio of raw materials according to the main components required for clinker, Portland cement usually also exhibits the clinker formed after sintering the cement raw material according to the standard of cement rate coefficient. The nature of the desire.

The cement rate coefficient includes the hydraulic modulus (HM), the enthalpy coefficient (SM), and the aluminum iron coefficient (IM), as detailed below:

Hydraulic coefficient (HM): The range may be between 1.7 and 2.3, preferably between 1.9 and 2.2.

Oxygen coefficient (SM): The range may be between 1.9 and 3.2, preferably between 2.1 and 2.7.

Aluminum iron coefficient (IM): The range may be between 1.5 and 2.5, preferably between 1.5 and 2.2.

The required cement ratio coefficient is achieved by the chemical composition obtained by X-ray Fluorescence Spectrometer (XRF) through an appropriate raw material ratio.

Instance

Testing of compressive strength, setting time and volume expansion of Portland cement clinker in accordance with CNS 61 specifications.

Example 1

CMP sludge A and CMP sludge B series completely replace the antimony ore used in traditional Portland cement raw materials, and chemical composition analysis of CMP sludge by X-ray Fluorescence Spectrometer (XRF) The results are shown in Table 2:

The XRF analysis results also show P ₂ O ₅ , Cr ₂ O ₃ , MnO, CuO, ZrO ₂ , Cl, Sm ₂ O ₃ , WO _3, etc., and the sum of these contents does not exceed 0.8%.

According to the composition of the components of Table 3, the raw materials were uniformly mixed and ground into green granules having a particle size of from 45 μm to 100 μm; the values listed in the tables are by weight.

The chemical composition analysis of raw materials was carried out by XRF. The test results are shown in Table 4:

According to the data of Table 4, the content of cerium in Sample A was about 0.365% by weight, and the cerium content in Sample B was about 0.103% by weight.

The test results show that the content of K ₂ O and Na ₂ O is greatly reduced by replacing the antimony ore with CMP sludge. The alkali content of the raw meal (up to 0.045%) is only the alkali content of the traditional Portland cement (0.507%). About 8.8% of the material is obviously very favorable for the preparation of cement clinker with low alkali content.

Example 2

The raw meal powder sample obtained in Example 1 was subjected to ingot treatment using a 25-ton tableting apparatus, and the cement clinker was sintered at a temperature of 1350 ° C for 6 hours to obtain cement clinker samples R-1, A-1 and B, respectively. -1, samples R-1, A-1 and B-1 were all in the form of black blocks. The sample was cooled and ground to obtain a clinker powder, and the mineral phase analysis was carried out by X-ray diffraction (XRD) (XRD model D2 phaser, Bruker): the sample scanning angle (2θ) was 10 -75°; scan rate 0.015°/s; scan time 0.35 seconds.

The analysis results show that the free lime (f-CaO) values are all below 1.0, and the mineral structures of samples A-1 and B-1 are tricalcium citrate (C ₃ S), dicalcium citrate (C ₂ S), and less. Partially tricalcium aluminate (C ₃ A), and aluminum iron tetracalcium (C ₄ AF), and no newly formed secondary mineral phase. Without wishing to be bound by theory, for example, when the raw material contains Cr ₂ O ₃ component, secondary mineral phases such as Ca ₄ A ₁₆ CrO ₄ and Ca ₆ A ₁₄ Cr ₂ O ₁₅ may be formed, which may affect the strength of the cement and increase the cement condensation. Time; however, both sample A-1 and sample B-1 did not contain such secondary mineral phases.

Comparing the XRD patterns, it is known that the mineral structures of samples A-1 and B-1 and sample R-1 are not significantly different, and all conform to the chemical composition specification of Portland cement type I, which means that CMP sludge is exposed to high temperature environment. After decomposition, it is recombined with CaO to form tricalcium citrate (C ₃ S), dicalcium citrate (C ₂ S), no newly formed secondary mineral phase, and no residual component which is not completely reacted. Feasibility of cement raw materials.

The chemical composition of semi-finished clinker was analyzed by XRF. The test results are shown in Table 5: The sample A-1 has a cerium content of about 0.365% by weight, and the sample B-1 has a cerium content of about 0.103% by weight; the remaining components are K ₂ O, Na ₂ O, P ₂ O ₅ , TiO ₂ , SrO, MnO, Cr. ₂ O ₃ , ZrO ₂ , Cl, etc., the total content is less than 1.5%. The samples are in compliance with CNS 61 specifications for the main components of Portland Type I cement.

Example 3

Samples R-1, A-1, and B-1 were made into the initial mixed cement mortars R-2, A-2, and B-2, respectively, and the setting time was determined by the Fisher apparatus and the initial setting time was determined. Cement initial setting time test results. In detail, when the penetration is 25mm, the required time is the initial setting time of the cement. According to the CNS 61 specification, the initial setting time of cement should range from 0.75 hours to 6.25 hours.

The test results showed that the initial mixed cement mortar R-2 began to coagulate reaction at 3.5 hours, the penetration degree began to decrease, and the initial setting time was 4.1 hours. The initial setting time of the initial mixed cement mortars A-2 and B-2 was 2.9 and 3.3 hours, the initial setting time of both is in line with the CNS 61 specification.

Example 4

Samples R-1, A-1 and B-1 were respectively co-milled with an appropriate amount of gypsum, and the finished powder particle size d _{50 was} controlled to be about 16 to 22 μm to prepare a hydraulic cement dip. According to the CNS 1010 hydraulic cement material compressive strength test method required by CNS 61 standard, the buckwheat material is made into a 5cm*5cm*5cm square test piece, and the test piece R-3, A-3 and B are obtained after 24 hours of demoulding. -3, and the test bodies R-3, A-3 and B-3 were placed in a constant temperature and humidity chamber at 23 ° C for water conservation, and the compressive strength tests were carried out for 1 day, 3 days, 7 days, and 28 days, respectively.

In addition, a thermocompression test was additionally performed. Test pieces R-3-1 and A-3-1 were obtained in the same manner after demolding, but were accelerated at a high temperature of 90 ° C, and a compressive strength test was performed one day later to represent late strength.

The test results are shown in Table 6.

The test results show that the compressive strength of hydraulic cement materials R-3, A-3 and B-3 can meet the requirements of CNS 61 for Portland type I cement; and high temperature accelerated curing sample A-3- 1 and B-3-1 were 296.4 and 321.0 kg/cm ² , respectively, that is, the cement obtained by using CMP sludge as a raw material had higher strength characteristics in the later stage. One of the possible reasons for this characteristic is that the CMP sludge has a smaller particle size than the general cement raw material, and the reaction of the high temperature liquid phase is relatively fast, so that the mineral crystallization is relatively fast and complete, so that the hydration, especially the high temperature, accelerates the curing. The data represents the strength of the later period is stronger than the general cement. Therefore, the use of CMP sludge as a raw material for cement not only reduces costs, but also improves the compressive strength of cement in the later stage.

Example 5

Samples R-1, A-1 and B-1 were respectively made into cement mortars R-4, A-4 and B-4, and placed in constant temperature and humidity for one day. The specimens were demolished and placed in a hot water environment of 90 °C. Accelerated curing is performed to assess volume stability. The test results are shown in Table 7.

Table 7: Test results of cement hot compressive expansion rate

At the initial 2 day age, it has been observed that the volume of the cement sample is swollen. However, under the test, the elongation at expansion of the test piece is maintained at about 0.020%.

The test results show that there is no significant difference in the coefficient of thermal expansion of cement mortars R-4, A-4 and B-4, indicating that CMP sludge instead of cement raw materials has no significant effect on the volume stability of cement, and also conforms to CNS 61 cement expansion. The rate standard (maximum value of 0.80%) confirms that the use of CMP sludge as a raw material for cement raw meal can also provide a compliance rate comparable to that of conventional cement.

It will be apparent to those skilled in the art that various modifications and changes can be made in the present invention without departing from the scope of the invention. In view of the above, it is intended that the present invention covers the modifications and variations of the present invention, and the modifications and variations are within the scope of the following claims and their equivalents.

Claims (10)

A Portland cement raw material comprising a calcareous material, a clay material, a ferrous material, and a chemical mechanical polishing (CMP) sludge, wherein the calcareous material has a calcium oxide content of at least 43% by weight; the clay material The material has an alumina content of at least 10% by weight; the ferrous material has an iron oxide content of at least 40% by weight; the CMP sludge comprises cerium oxide and cerium oxide, and the cerium oxide content is at least 60% by weight, and low a fluorine content of 40% by weight; and wherein the cement raw meal contains at least 0.024% by weight of rhodium. The Portland cement raw material of claim 1 is selected from the group consisting of Portland type I, type IA, type II, type IIA, type II (MH), type II (MH) A, type III, type IIIA, Type IV and V cement raw materials. The Portland cement raw material of claim 1, wherein the raw material has a base content of 0.5% by weight or less. A Portland cement clinker comprising tricalcium citrate, dicalcium citrate, tricalcium aluminate, a tetracalcium aluminate mineral phase, characterized by containing less than 0.04% by weight of fluorine and containing at least 0.024% by weight. The Portland cement clinker of claim 4 has an alkali content of at most 0.6% by weight. A method of producing Portland cement clinker, which comprises the step of sintering the Portland cement raw meal of any one of claims 1 to 3 of the rotary kiln. The method of claim 6 further comprising the step of treating the dried CMP sludge. A concrete comprising Portland cement clinker according to any one of claims 4 or 5 or Portland cement clinker, water and additives prepared by the method of claim 6 or 7. The concrete of claim 8, wherein the additive comprises gypsum. The concrete of claim 8 or 9, further comprising at least one of an aggregate and a spike.