CN1080747C - 纸张脱墨厂残渣中无机填料的回收 - Google Patents
纸张脱墨厂残渣中无机填料的回收 Download PDFInfo
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- CN1080747C CN1080747C CN96192559A CN96192559A CN1080747C CN 1080747 C CN1080747 C CN 1080747C CN 96192559 A CN96192559 A CN 96192559A CN 96192559 A CN96192559 A CN 96192559A CN 1080747 C CN1080747 C CN 1080747C
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- 239000010936 titanium Substances 0.000 claims 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 18
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
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- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- YTCQFLFGFXZUSN-BAQGIRSFSA-N microline Chemical compound OC12OC3(C)COC2(O)C(C(/Cl)=C/C)=CC(=O)C21C3C2 YTCQFLFGFXZUSN-BAQGIRSFSA-N 0.000 description 1
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- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
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Classifications
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- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- D—TEXTILES; PAPER
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/51—Particles with a specific particle size distribution
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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
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- Paper (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
一种回收在废纸脱墨产生的废料中含有的无机颜料的方法。在含氧气氛中把脱墨残渣加热到足够高的温度,使得其中存在的所有有机碳氢化合物完全氧化。在该方法中还可以产生热、水、和二氧化碳,而且可以收集并再利用所产生的热、水和二氧化碳。燃烧引起化学反应的发生,从而使脱墨残渣中所含的原始的颜料转变成新的、稳定的矿物形式。燃烧的灰分基本是钙黄长石(Ca2Al2SiO7)、钙长石(CaAl2Si2O8)和钙钛矿(CaTiO3)。把含有混合矿物相的灰分加入到反应器中,在反应器中使二氧化碳鼓泡通过氢氧化钙的水基料浆,产生沉淀碳酸钙(PCC)。因为在灰分中的矿物相含有钙作为其晶体结构的一部分,所以,PCC将在灰分颗粒上沉淀并长大。这使得在“回收”PCC颜料中含有灰分“内核”。回收PCC的性能类似于纯PCC。
Description
本发明涉及纸张脱墨厂残渣中无机填料的回收。这样的填料一般是由混合颜料(粘土、碳酸钙、二氧化钛等)、水、纤维素、墨、调色剂、粘合剂等组成的废料的复杂混合物的一部分。一般来说,或者焚烧这些废料的有机组分的可燃物,或者把它们埋在坑中。本发明描述使这些无机填料变得适合于用作通过使石灰乳(Ca(OH)2)与二氧化碳气体反应生产沉淀碳酸钙(PCC)过程中的原料和基质的方法。
废纸的回收一般包括通过以适合于脱墨厂的任何方式进行的一系列步骤把可用的纸浆纤维从纸张的其它组分(如无机填料、印刷油墨、激光调色剂颗粒和粘合剂等)中分离出来。无论采用哪种特定的回收方法,总会产生两种物料:(1)纸浆纤维,叫做“再生”纤维,可以卖给造纸厂,重新作为造纸原料,(2)复合废料,包括作为脱墨过程的一部分除去的组分的混合物。这种复合废料叫做脱墨残渣(DIR)。
产生的DIR的量将随着进料的废纸质量和回收方法的种类而变化。典型地,按干基计算,DIR的比例是脱墨前的原始废纸重量的15~40%。由于DIR是以湿的状态生产的,在废料离开脱墨过程之前,应该尽可能多地除去水以降低处理和运输成本。一般来说,把废料压到约含有50%的固体。因此,对应每100吨处理的废纸,将产生30~80吨湿的DIR,其中一半是水。到1996年底,北美的脱墨厂将回收350万吨以上的废纸,因此,将产生100万吨以上的湿残渣。
在脱墨厂与造纸厂结合在一起操作的情况下,通常在造纸厂的白液回收锅炉中焚烧DIR的可燃组分。但是由于其含水量高,DIR是低级的、无效率的燃料。在非整体的脱墨厂中,所说的残渣最常见的命运是填地。填地是不受欢迎的,因为其成本高而且对环境有害。因此,需要通过再利用残渣混合物中存在的无机填料和/或其它组分以减少在脱墨厂产生的废料的体积。
许多级别的纸张中含有功能性的无机颜料,如高岭土、碳酸钙、二氧化钛、硅酸盐等,它们是在造纸时掺入的。还没有实用的方法把无机颜料从废料的有机组分中分离出来,以便使所说的无机颜料可以在产品或造纸过程中再利用。
以前,造纸或回收废纸产生的废料被焚烧,焚烧后的残渣堆放在堆坑中或用于生产一般用于建筑结构中的骨料。这种残留的灰分一般构成DIR原始重量的15~20%。
在美国专利No.4,932,336中,湿的脱水后收集到的固体产物主要由纤维素质物质组成(木质和纤维素质纤维),残渣主要由在回收之前从废纸中分离的塑料碎片组成,分别回收所说的固体产物和残渣。把所收集的产物干燥到残余含水量不大于产物的25wt%,连续地层化使其形成连续前进的层。把一层残渣沉积在产物层上形成连续前进的双层的床,在从底部鼓入含有空气的气体时,所说的双层的床燃烧。在该过程中,破坏了产物和残渣,产生了燃烧的气体,回收到熔渣。在该过程中产生的飞灰可以加入到熔渣中以免其释放到环境中,或者把所说的熔渣堆放在坑中,或用作结构材料。燃烧气体产生的热量也可以用作热源,尤其是用于产生蒸汽。
美国专利No.5,018,459提出了一种用于回收作为纸张、纸板以及相应的材料制造过程中的废料产生的纸浆残渣的方法和设备。把纸浆残渣连续地喂入800~3500°F的回转窑。如果温度保持在2400°F以上,将会破坏掉在焚烧过程中产生的危险物质,如二噁类化合物。混合催化剂,一般为酪蛋白或大豆蛋白,和木质纸浆纤维与所说的纸浆残渣一起燃烧。所得的焚烧产物基本由碳酸盐颗粒组成,可以用作制造沥青、沥青涂层、密封胶、陶瓷、混凝土、水泥管、粘土管、结构砌块和砖的无机填料结合剂,或者用作泄漏的油的吸附剂。在美国专利No.5,054,406中,把纸浆残渣的焚烧产物的15~25wt%与粘土混合形成阻水材料,可以用作覆盖和密封堆放坑。
美国专利No.4,769,149提出了一种从废料和残渣回收能量的方法,包括废料的细菌分解,然后进行焚烧,其中,在细菌分解过程中产生的甲烷气用于加热所说的焚烧炉。然后燃烧释放的热量可以用于需要热量的工业过程中。
欧洲专利申请No.0 604 095提出了一种处理颗粒废料的水基稀悬浮液的方法,如造纸厂污水中发现的物质。用高岭土作为典型的废料的实例。该过程包括使所说的颗粒物料的水基悬浮液中碱土金属碳酸盐沉淀,如碳酸钙,使得在过程开始时存在的颗粒物料掺入碱土金属碳酸盐沉淀中。EPA0604 095的图1表示了在沉淀的碳酸钙颗粒聚集体中混杂的扁平的“板状”高岭土颗粒的扫描电子显微照片。所得的碳酸钙和混杂的粘土颗粒的聚集体可以用作纸张填料或颜料。
但是,仍然需要一定的方法回收DIR,使其产生有用的产品而不是作为填地的物料。本发明提供解决这个问题的一种方法。
本发明提供一种回收和再利用废纸脱墨并加工成再生纸浆纤维时产生的残渣中的无机颜料的方法。这种方法包括在含氧气氛中把所说的残渣加热到一定温度,该温度应该足够高,使得在所说的脱墨残渣中,除了从废纸中存在的不可燃无机颜料形成灰分以外,把所有碳氢化合物氧化产生热、二氧化碳和水。在本发明中,把燃烧后的无机灰分与氧化钙和水混合形成氢氧化钙和灰分的泥浆。含有二氧化碳的气体可以是过滤并冷却的烟囱气体,使其鼓泡通过所说的泥浆混合物,随着碳酸钙的沉淀,碳酸钙完全覆盖在灰分颗粒的表面上,灰分颗粒作为基体,成为沉淀的成核位置并使沉淀长大。在PCC表面下的无机灰分的核对所谓的“纯粹的”PCC表现出的光学和物理性质几乎没有或完全没有影响,因此“回收”的PCC在大多数需要PCC的过程或产品中可以用作纯PCC的替代品,而对产品质量几乎没有或完全没有影响。在一般过程中,燃烧产生的热、二氧化碳和水可以收集和回收使用。用这种方法,可以大量减少典型的脱墨厂的废料。
图1是本发明的过程的流程图。
本发明的一个优选的实施方案表示于图1。在含氧气氛中把脱墨废料加热到足够高的温度,一般为800~1200℃,使得把所有的有机碳氢化合物氧化,并完全有效地焚烧。这种燃烧的基本产物是热、二氧化碳、水和无机灰分。如果需要,先研磨所说的无机灰分,然后通过把所说的无机灰分与氢氧化钙(Ca(OH)2)的水基料浆混合制备水基料浆,所说的氢氧化钙水基料浆是通过向水中加入石灰(CaO)形成的。氢氧化钙料浆也叫做石灰乳、消化石灰或者简称消石灰。含有二氧化碳的气体混合物鼓泡通过所说的料浆,其中,氢氧化钙和二氧化碳反应形成PCC。控制反应参数,如温度、气体浓度和加入速度、消石灰浓度等使得产生要求的PCC晶体尺寸和形态。在本发明中,已经发现所说的PCC在存在于消石灰中的无机灰分的表面沉淀并长大。有利的是,回收加热过程的燃烧产物,水用于形成浆料,二氧化碳用于沉淀PCC、热量用于干燥焚烧前的另外的DIR。在反应完成时,无机灰分的表面已经涂敷了PCC形成复合材料颗粒,并且与类似尺寸的纯PCC具有基本相同的光学性质和物理性质。
在本发明的另一个实施方案中,向干燥的、未消化的石灰(CaO)中加入DIR燃烧产生的无机灰分。然后向该混合物中加入多余的水分形成无机灰分和氢氧化钙的浆料,然后进行如上所述的碳酸盐化反应。
在本发明的第三个实施方案中,残渣的燃烧是作为煅烧过程的一部分进行的,其中,把石灰石转变为石灰。这是可能的,因为石灰石煅烧需要的温度类似于所说的DIR高效率燃烧所需要的温度。湿的DIR和石灰石混合喂入石灰窑,调整其相对含量使得在煅烧产物中的无机灰分和石灰的比例对于消化和碳酸盐化是正确的比例。
还可以认识到通过DIR中的碳氢化合物组分的燃烧产生的,通常从烟筒排出的热量和二氧化碳是可以收集并回收或者重新送入一般过程的前面部分或后面的部分。例如,热量可以回收到所说的窑中帮助在燃烧发生前需要进行的残渣的干燥。由于焚烧残渣的碳氢化合物组分产生的二氧化碳可以收集起来用于使氢氧化钙碳酸盐化成为PCC。
无机灰分可以用沉淀的碳酸钙涂敷或覆盖的事实是意想不到的。在本发明中,这是可能的,因为由DIR的燃烧得到的无机灰分是通过比简单的碳酸盐化更复杂的化学反应形成的。例如,在把高岭土(H2Al2Si2O8·H2O)或碳酸钙在窑炉中加热到高温时,产生煅烧的无机物相,即煅烧粘土或氧化钙。在本发明中,已经发现混合的无机颜料在高温下反应形成新的、稳定的无机物相。在以各种比例混合碳酸钙、高岭土和二氧化钛并加热到800~1200℃,一般为1000℃时,会产生各种比例的两种、三种或更多的新相,包括钙黄长石(Ca2AlSiO7)和/或钙长石(CaAl2Si2O8)和一些钙钛矿(CaTiO3)。形成的每相的相对含量取决于在原始混合物中存在的每种无机物的含量和燃烧温度。相信这些新相为碳酸钙的直接沉淀提供了成核位置,碳酸钙涂敷或者沉积在灰分的表面。
可以容易地看出,这些无机物相含有构成未煅烧的无机颜料相同的元素,即钙、铝、硅和氧。相信燃烧的高温引起这些物质反应并重排形成热力学稳定的无机物相。在钙黄长石、钙长石和钙钛矿晶格中的钙原子的存在使得这些物质适合于作为基质,从而使碳酸钙在其上成核与生长。碳酸钙直接沉淀在所说的灰分颗粒的表面上,用与灰分结合的PCC层完全覆盖或涂敷所说的颗粒。本发明的方法不仅仅是通过形成与周围的灰分颗粒结合在一起的PCC颗粒捕获、限制或带走所说的灰分,而且实际上直接沉淀碳酸盐到灰分表面形成由无机灰分内部部分和PCC外部部分构成的复合颗粒。实际上,所说的灰分作为籽晶为碳酸钙沉淀提供成核位置。一般来说,内部的灰分部分可以占颗粒重量的约50%。在一个典型的颗粒中,灰分部分可以在5~30%范围内,优选的是在10~25%之间。当然,最大量的灰分是希望的,因为可以回收最大量的灰分。在这方面,认为50∶50的灰分:碳酸钙颗粒比是最佳的比例。
当脱墨残渣是废料时,所说的组合物的结构将会发生变化。如果必要,仍然可以认识到在焚烧前可以向废料中加入适量的粘土、二氧化钛、碳酸钙或其它合适的物质,以便在燃烧过程中形成合适的无机物相。
有理由相信在本发明的回收PCC中可以发现的钙黄长石、钙长石和钙钛矿的量低于通过这里描述的方法收集和分析的物料损失所说明的量。如果发生的损失不能解释,那么这些无机物相中的一些或全部有可能在反应过程中转变成PCC。这是可以发生的,因为在氢氧化钙的含水料浆中pH较高,或者由于在碳酸盐化过程中存在其它条件。
本发明的“回收”PCC,单独的或者与所谓的纯PCC一起,可以用于使用纯PCC的大多数用途中。PCC通常用于要求高级的功能性无机颜料的印刷和书写纸的生产中,在大多数这样的用途中,回收的PCC可以单独使用或与纯PCC混合使用。在一个典型的应用中,PCC的量约在所说的混合物的1%~50%范围内。回收的PCC也可以用于现在使用纯PCC的涂料和填充的聚合物应用中。由于发观了纯PCC的其它用途,可能会发现回收的PCC也是适用的。实例表明了所得的回收PCC质量,在该技术中具有普通技术人员可以容易地确定回收PCC适用的用途。可以混合使用回收PCC和纯PCC,如果需要或者有必要,两者在作为功能添加剂时在处理和加工方面是相容的。
用Micromeritics Flowcarb 2300可以得到回收的PCC和纯PCC颗粒的表面积,Micromeritics Flowcarb 2300用氮气作为吸附气体,采用BET理论进行测量。用约0.1%的羰基化聚合电解质(Daxad 30)作为分散剂,在产品的约3%的水悬浮液中,用Sedigraph Model 5100通过沉降技术测定颗粒尺寸。用Hunter LabScan测定干基亮度。
用在pH值为7的蒸馏水中打浆成为400 Canadian Standard Freeness(CSF)的配料为75%的漂白硬木纸浆和25%的漂白软木硫酸盐纸浆,用Formax Sheet成形机(Adirondack Machine Corporation制造的Noble andWood型)制备60g/m2的纸张。纸浆浓度为0.3125%。向纸浆中添加0.25%的合成上胶剂(烷基乙烯酮二聚物),相当于5磅/吨纸。向所说的纸浆配料中添加填料得到要求的填料添加量。向所说的纸浆中添加0.05%的保形助剂(高密度阳离子聚丙烯酰胺)相当于1磅/吨纸。在试验前,把所说的纸张在50%的相对湿度,23℃下保持最少24小时。
用TAPPI试验方法T452-om92测量TAPPI亮度。根据TAPPI试验方法T425-om91测定TAPPI不透明性。根据Parker Print-Surf法测定气孔率。根据TAPPI试验方法UM-403测定Scott Bond。根据TAPPI试验方法T494-om88测定断裂长度。
通过Hercules Size试验(HST)测定液体通过纸张的渗透来试验上胶性能。HST是本发明中用来测定纸张上胶程度的试验方法。所说的试验在Model KA或KC型Hercules上胶试验机上进行,使用的试验方法是TAPPIMethod T-530 PM-89。
实施例
下面的非限制性实施例仅用于示例说明本发明的优选的实施方案,不能作为本发明的限制,本发明的范围由附加的权利要求书确定。
用两种来自工业脱墨厂的湿脱墨残渣制备回收PCC。得到的试样含有约50wt%的水分。把试样在烘箱内在100℃下干燥,用X射线衍射分析每个试样的干基固体的组成。分析结果列于表1。所有的数值用干基固体的重量百分数表示。
表1
I II有机碳氢化 57-59 <50碳酸钙(CaCO3) 11-12 30-40高岭石 14-15 10-15(H2Al2Si2O8·H2O)锐钛矿(TiO2) 2-4 2-4无定形相 <5 未测滑 0.5-1 0.5-1金红石(TiO2) 0.5-1 0.5-1α-石英 0.5-1 未测
实施例I
在马弗炉中在900℃把残渣试样I焚烧2小时。从炉中回收的灰分用锤式粉碎机打开团聚,并用X射线衍射(XRD)进行分析。所说的XRD分析结果列于表2。所说的数值是用灰分总量的重量的百分数给出的近似范围。
表2钙黄长石(Ca2Al2SiO7) 85-90钙长石(CaAl2Si2O8) <5钙钛矿(CaTiO3) 5-10
为了形成氢氧化钙料浆,向229.6克CaO中加入1607.2克水,在4升的带有变速搅拌器的不锈钢反应器中强烈搅拌所说的混合物。在进行所说的过程之前,把所说的氢氧化钙料浆过60目筛。向所说的料浆中加入57.4克表2的无机灰分,并把料浆的温度调整到35.2℃。使含有二氧化碳的气体(15%浓度于空气中)鼓泡通过强烈搅拌的这种混合物,直至在pH为8时在115分钟使所说的反应完成。把所得的产物过325目筛除去细砂,称量回收的+325目筛残渣,发现仅有10.661克。进行所说的回收PCC的扫描电镜(SEM)分析和物理分析。通过用PCC涂敷表2的无机灰分制备的干基回收的PCC产品的物理性质表示于表3。
表3
通过Sediagraph 5100测定的尺寸分布:
小于90% 5.89μm
小于50% 1.91
小于20% 1.17
小于10% 0.79BET比表面积: 8.7m2/gHunter颜色组成(颜料):
L(亮度) 95.9
a 0.2
b 1.8通过SEM测得的形貌 偏三角面体
用硫酸盐纤维配料在手抄纸研究中试验实施例I中生产的回收PCC在纸中的性能。手抄纸研究的结果列于表7,结果表明本发明的回收PCC可以用与纯PCC一样的方法有效地用于造纸中。
掺入回收PCC和纯PCC的手抄纸的TAPPI亮度测定表明用回收PCC可以获得高的纸张亮度。掺入实施例I的回收PCC的纸张的TAPPI亮度在掺入纯PCC的纸张的2个百分点范围内。因此,回收的PCC可以在不掺入纯PCC时用于不要求最大亮度的应用中。要求最大亮度和需要控制纸张亮度的用途的要求可以通过使用纯PCC和回收的PCC的混合物来满足。用于高质量的纸张中的纯PCC和回收PCC的优选的混合物在10%~50%之间。
掺入回收PCC的手抄纸和掺入纯PCC的手抄纸的TAPPI不透明性的差别约为1个百分点,这在这些测量的统计精度范围内。所以,本发明的掺入回收PCC的纸张的外观基本相当于掺入纯PCC的纸张。
如用HST试验测量的,在比较相应尺寸的填料时,掺入回收PCC的手抄纸的耐水性相当于掺入纯PCC作为填料的手抄纸的耐水性。
掺入回收PCC的手抄纸强度基本相当于或比掺入纯PCC的手抄纸略好。但是,这些手抄纸的厚度略大于掺入纯PCC的纸张厚度。
最后,回收PCC纸张的气孔率略高于纯PCC,但是不会高到表现出明显的缺点。
实施例II
把3份脱墨残渣试样II(表1)与4份开采的石灰石混合并放在实验回转窑中。所说的回转窑是烧煤气的,大约1.5米长,直径约为16.5cm。所说的窑炉确定在1150℃操作,燃烧的名义时间约为45分钟。燃烧后,从所说的窑炉中收集所说的石灰/灰分混合物,并用XRD分析。结果列于表4。所说的结果以石灰石和脱墨残渣的总重量的重量百分数给出。
表4
石灰(CaO) 70-80
钙黄长石(Ca2Al2SiO7) 10-15
钙长石(CaAl2Si2O8) 7-10
钙钛矿(CaTiO3) 1-2
微料长石(KAlSi3O8) 1-2
α-石英 0.5-1
为了形成氢氧化钙和无机灰分的料浆,向287克表4的物料中加入2009克水,在4升的装有变速搅拌器的不锈钢反应器中剧烈搅拌所说的混合物。在继续进行反应之前,把所得的氢氧化钙/无机灰分的料浆过60目筛,从筛子上收集到0.05克残渣。把料浆的温度调整到35.5℃,使含有二氧化碳的气体(在空气中含有15%)在剧烈搅拌的条件下鼓泡通过所说的混合物直至料浆的pH值为8时在121分钟结束后反应完成。回收的PCC料浆过325目筛除去细砂和其它杂质,收集到24.7克+325目的残渣。用XRD分析回收的PCC和+325目的细砂,结果列于表5。所说的结果以每种物料的重量百分数给出。
表5
回收PCC +325目的残渣碳酸钙(CaCO3) 89-94 <0.5羟钙石(Ca(OH)2) <0.5 <0.5钙黄长石 4-7 20-25(Ca2Al2SiO7)钙长石(CaAl2Si2O8) 0.5-1 5-10钙钛矿(CaTiO3) 1-2 20-25α-石英 0.5-1 20-25微斜长石(KAlSi3O8) <0.5 20-25
表5的干基“回收”PCC产品的物料特性列于表6。
表6
通过Sedigraph 5100的尺寸分布:
小于90% 2.73μm
小于50% 1.39
小于20% 0.96
小于10% 0.71
BET比表面积: 14.8m2/g
Hunter颜色组成(颜料):
L(亮度) 97.2
a 0.0
b 1.1
通过SEM测得的形貌: 偏三角面体
也用硫酸盐纤维配料在手抄纸研究中试验实施例II中生产的回收PCC在纸张中的性能。而且,试验结果列于表7,结果表明本发明的回收PCC可以用与纯PCC相同的方法有效地用于造纸中。
和实施例I一样,掺入回收PCC和纯PCC的手抄纸的TAPPI亮度的测量表明用回收的PCC可以获得高的纸张亮度。但是,掺入实施例II的回收PCC的手抄纸的亮度是相当的,但是其填料含量略高于掺入纯PCC的手抄纸。
类似地,掺入回收PCC的手抄纸的TAPPI不透明度相当于掺入纯PCC的手抄纸,但是填料含量稍高。所以,本发明的掺入回收PCC的纸张的外观基本相当于掺入纯PCC的纸张。
如在HST试验中测量的,在比较相应尺寸的填料时,掺入回收PCC的手抄纸的耐水性相当于掺入纯PCC作为填料的手抄纸。
掺入回收PCC和纯PCC的纸张的强度略低于控制值,可能是由于填料量的差别。
最后,在实施例II中,回收PCC的纸张的气孔率略低于纯PCC纸张的气孔率,但是很好地在可以接受的范围内。
表7
回收PCC 回收PCC 纯PCC 纯PCC颜料 实施例I 实施例II 2.18μm 1.23μm填料百分数 14.4 17.4 15.8 14.7不透明度 87.5 88.6 86.8 88.6亮度 84.3 86.2 86.5 86.4断裂长度 2425 1946 2189 2242HERCULES 105 1 101 2上胶性SCOTT BOND 53 46 52 51气孔率 2203 1801 1958 2023
明显的是本文提出的发明已达到上述目的,熟悉该技术的人可以提出许多修改和实施方案是值得注意的。附属的权利要求书打算覆盖所有的这样的修改和实施方案,以落入本发明的实质和范围内。
Claims (10)
1、一种复合颗粒物料,包括一个无机矿物物料灰分的内部部分,和一个碳酸钙的外部部分,其中,所说的无机矿物物料灰分包括焚烧废纸脱墨残渣得到的灰分,所说的碳酸钙沉淀在所说的无机矿物物料灰分的内部部分的表面上。
2、根据权利要求1的复合颗粒物料,其中,所说的无机矿物物料灰分包括钙黄长石、钙长石、钙钛矿或其混合物。
3、一种纸张,包括纤维素质纤维和权利要求1的复合颗粒物料。
4、根据权利要求3的纸张,还含有纯的沉淀碳酸钙,其中,纯的沉淀碳酸钙与复合颗粒物料的比例在99∶1~1∶1之间。
5、一种制造权利要求1的复合颗粒物料的方法,包括:
形成一种氢氧化钙和在至少800℃的温度下焚烧废纸脱墨残渣得到的灰分颗粒的含水料浆;
通过使含二氧化碳的气体鼓泡通过所说的料浆直接在灰分颗粒上沉淀碳酸钙;
回收所说的沉淀碳酸钙颗粒。
6、根据权利要求5的方法,还包括在焚烧前向所说的废纸脱墨残渣中加入至少一种钙、铝或钛的化合物或其混合物。
7、根据权利要求6的方法,其中,所说的化合物是碳酸钙、二氧化钛、粘土、或其混合物。
8、根据权利要求5、6或7的方法,还包括形成一种氢氧化钙和水的混合物,向所说的混合物中加入所说的灰分形成料浆。
9、根据权利要求5、6或7的方法,还包括把所说的灰分与石灰混合,然后向所说的灰分和石灰的混合物加水形成料浆。
10、根据权利要求5、6或7的方法,还包括把废纸脱墨残渣与石灰石混合,在石灰窑中煅烧所说的混合物同时焚烧所说的废纸脱墨残渣得到灰分和石灰颗粒,再向所说的颗粒中加水形成所说的料浆。
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CN1178545A (zh) | 1998-04-08 |
PL322087A1 (en) | 1998-01-05 |
AU708961B2 (en) | 1999-08-19 |
JP3274141B2 (ja) | 2002-04-15 |
WO1996028517A1 (en) | 1996-09-19 |
US5759258A (en) | 1998-06-02 |
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HUP9800828A3 (en) | 1998-12-28 |
CA2215297C (en) | 2007-02-27 |
EP0815175A1 (en) | 1998-01-07 |
JPH11502877A (ja) | 1999-03-09 |
HUP9800828A2 (hu) | 1998-08-28 |
DE69608427D1 (de) | 2000-06-21 |
AR001257A1 (es) | 1997-09-24 |
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PL183380B1 (pl) | 2002-06-28 |
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ATE193040T1 (de) | 2000-06-15 |
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NZ304674A (en) | 1999-05-28 |
KR19980702964A (ko) | 1998-09-05 |
SK122097A3 (en) | 1998-06-03 |
MX9707039A (es) | 1997-11-29 |
ES2149458T3 (es) | 2000-11-01 |
DE69608427T2 (de) | 2001-01-11 |
BR9607369A (pt) | 1997-12-30 |
CZ261697A3 (cs) | 1998-04-15 |
NO974222D0 (no) | 1997-09-12 |
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