CN103468333B - OILY water sludge coke slurry and preparation method - Google Patents

OILY water sludge coke slurry and preparation method Download PDF

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CN103468333B
CN103468333B CN201210184886.0A CN201210184886A CN103468333B CN 103468333 B CN103468333 B CN 103468333B CN 201210184886 A CN201210184886 A CN 201210184886A CN 103468333 B CN103468333 B CN 103468333B
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water
sludge
coke
oily sludge
slurry
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CN103468333A (en
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刘海峰
付兴国
刘银东
代正华
李伟锋
高飞
许建良
张艳梅
王辅臣
于广锁
王亦飞
龚欣
郭晓镭
郭庆华
陈雪莉
周志杰
王兴军
张强
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中国石油天然气股份有限公司
华东理工大学
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Abstract

本发明涉及一种含油污泥水焦浆及其制备方法;以质量100%计,由以下各组分组成:石油焦50%~75%;含油污泥0.1%~15%;分散剂0.001%~1%;含油污泥改性药剂0%~1%;余量为水;分散剂为萘磺酸盐类、聚羧酸盐类、腐植酸类或木质素磺酸盐类表面活性剂中的一种或几种物质混合物;含油污泥改性药剂为二价或三价的铁、铝或钙的金属离子无机盐类;含油污泥为原油在开采、运输、加工过程中形成的油、水混合物;本方法所制备的含油污泥水焦浆具有热值高,流动性与稳定性好,易于存储、输送与雾化,可作为燃烧或气化原料,具有规模化应用前景。 The present invention relates to a method for preparing aqueous coke slurry and oily sludge; 100% by mass, consists of the following components: 50% petroleum coke and 75%; oily sludge from 0.1% to 15%; dispersant 0.001% to 1%; oily sludge modification agents from 0% to 1%; the balance being water; dispersing agent is a naphthalene sulfonates, polycarboxylates, lignin sulfonates or humic acid surfactant or a mixture of several substances; oily sludge modifying agent is a divalent or trivalent iron, aluminum or calcium ions metal inorganic salt; crude oil content sludge formation in the mining, transport, processing , water mixture; oily sludge coke water slurry prepared by the present process has a high calorific value, good fluidity and stability, easy to store, transport and atomization, combustion or gasification as feedstock, a large-scale application.

Description

一种含油污泥水焦浆及其制备方法 OILY water sludge coke slurry and preparation method

技术领域 FIELD

[0001] 本发明涉及一种高浓度、高稳定性含油污泥、石油焦混合浆体及其制备方法,具体涉及一种高稳定性含油污泥水焦浆及其制备方法。 [0001] The present invention relates to a high-concentration, high stability oil sludge, petroleum coke slurry mixing and preparation method, particularly relates to a water slurry of a high power stability of oil sludge and its preparation method.

背景技术 Background technique

[0002] 石油焦是石油炼化企业延迟焦化装置在生产轻质油品是的副产物,物理形态与煤相似。 [0002] Petroleum coke is a delayed coker oil refining companies in the production of light oil is a by-product, similar to the physical form of coal. 石油焦碳含量高、热值高、挥发分低,性质与无烟煤相近。 High content of petroleum coke, high calorific value, low volatile, anthracite with similar properties. 其低位发热量约为普通动力煤的1.5〜2倍。 Its low calorific is about 1.5~2 times the normal thermal coal. 但水焦制浆存在稳定性差的缺点,生产过程中需采用添加稳定剂方法增加水焦浆稳定时间。 But the water power pulp disadvantage of poor stability, the production process requires the use of a method of adding a stabilizer to increase the water coke slurry stabilization time. 稳定剂的使用不仅会增加水焦浆制浆成本,且会使浆体表观粘度上升,降低石油焦成浆浓度与使用的经济性。 Stabilizers will not only increase the cost of water power pulp slurry, and the apparent viscosity of the slurry will increase, reducing the petroleum coke slurry concentration using economy. 且水焦浆很容易形成胀塑性流体,这与理想浆态燃料的屈服假塑性浆体性能相背。 Coke slurry and the water is easy to form dilatant fluid, which contrary to yield pseudoplastic properties of the slurry over the slurry fuel. 又由于石油焦挥发分低、活性较差,较难点火且燃烧、气化利用效率不高。 Also, because petroleum coke low volatile, less reactive, difficult ignition and combustion, gasification efficiency is not high.

[0003] 原油在开采、运输、加工过程中均会产生大量的含油污泥。 [0003] In crude oil production, transportation, processing will produce a lot of oil sludge. 这种污泥产量大、含油量高、重质油组分高,并且还含有大量的苯系物、酚类、蒽、芘等恶臭有毒物质和重金属,已于1998年7月1日起被列入《国家危险废物名录》,属有毒、易燃废物。 This sludge yield, high oil content, high heavy oil component, and also contains a lot of toxic benzene malodorous substances and heavy metals was phenols, anthracene, pyrene, it was 1998 on July 1 was included in the "national List of hazardous wastes", is a toxic, flammable waste. 国内外处理含油污泥的方法主要有:溶剂萃取,生物处理,焚烧等。 The method of treatment of oil sludge and abroad are: solvent extraction, biological treatment, incineration and the like. 由于含油污泥中往往油类乳化充分,很难实现油-水的有效分离。 Since the oily sludge is often sufficient oil emulsion, the oil is difficult to achieve - effective separation of water. 而且含油污泥水分含量高无法支持自燃,且导致含油污泥排放量增加, 处理成本上升。 And oily sludge moisture content can not support high spontaneous combustion, resulting in increased oil sludge and emissions, increased treatment costs. 目前含油污泥尚无安全可靠,效率收益兼顾的高效处理法,是石化行业亟需解决的一大难题。 Oily sludge currently no safe and reliable, and efficient approach taking into account the efficiency gains, and the petrochemical industry is needed to solve a major problem.

发明内容 SUMMARY

[0004]本发明的目的是提供一种含油污泥水焦浆及其制备方法,提出将含油污泥与石油焦混合制备含油污泥水焦浆。 [0004] The object of the present invention is to provide one kind of water-oily sludge and coke slurry preparation method proposed prepared by mixing petroleum coke oily sludge and oil sludge coke water slurry. 加入含油污泥后,水浆稳定性显著提高,可完全满足生产需要。 After addition of sludge, significantly improved the stability of aqueous slurry, can fully meet production needs. 同时该过程可充分利用含油污泥中的水分、热量。 Meanwhile, the process may take advantage of oily sludge water, heat. 含油污泥中轻质烃类等有机物可增加浆体燃料中的挥发分,与热值,弥补水焦浆挥发分低难于燃烧与气化的缺点。 Oily sludge and other light hydrocarbons, volatile organic compounds increase the slurry fuel, and heating value, to compensate for the disadvantages of volatile water coke slurry and partial combustion gasification of a low difficulty. 制备的污泥水焦浆可泵送,并易于雾化、贮存与稳定着火燃烧与气化。 Water sludge coke slurry prepared pumpable and readily atomized, and storage stability ignition combustion and gasification. 在不降低水焦浆可燃组分浓度的基础之上,大幅度提高水焦浆的稳定性。 Without reducing the water slurry coke concentration on the combustible components, greatly improve the stability of the aqueous slurry of coke. 同时直接利用含油污泥中的能量,实现石油焦资源与含油污泥的高效利用。 While energy directly oily sludge, petroleum coke efficient use of resources and oily sludge.

[0005]本发明所述的含油污泥水焦浆,以质量100%计由下各组分组成: [0005] The present invention is oil sludge coke slurry water to 100% by mass of the components by the following composition:

[0006] 石油焦50%〜75% ;含油污泥〇. 1%〜15% ;分散剂0.001%〜1% ;含油污泥改性药剂0%〜1 % ;余量为水。 [0006] Petroleum coke 50% ~ 75%;. Oily sludge ~ 15% 1% billion; dispersant of 0.001% ~ 1%; oily sludge modification agents 0% ~ 1%; the balance being water.

[0007]所述的石油焦为石油加工后形成的高含碳固态副产物。 [0007] The high carbon content of the solid by-products formed after petroleum coke is petroleum processing.

[0008]所述的含油污泥为工业生产过程中形成的任意比例混合的油、水混合物,其中还可能含有乳化剂、固体颗粒、无机盐在内的一种或几种。 [0008] The oil-containing industrial sludge arbitrary ratio formed during mixing oil, water mixture, which may also contain one or more emulsifying agents, solid particles, including inorganic salts.

[0009]所述的含油污泥水焦浆分散剂为萘磺酸盐类、聚羧酸盐类、腐植酸类或木质素磺酸盐类表面活性剂中的一种或几种物质混合物。 [0009] The aqueous oily sludge coke slurry naphthalene sulfonate dispersant is a substance or a mixture of several polycarboxylates, lignin sulfonates or humic acid surface active agents.

[0010]所述含油污泥改性剂为铁、铝、钙等二价、三价金属离子的无机盐。 [0010] The oily sludge modifier is iron, aluminum, calcium divalent, trivalent metal ions of inorganic salts.

[0011]本发明所述的含油污泥水焦浆的制备方法,包括以下步骤: [0011] Preparation of the oily sludge coke water slurry of the present invention, comprising the steps of:

[0012] a •含油污泥与含油污泥改性药剂混合搅拌并加水稀释,制备改性含油污泥混合液; [0012] a • oily sludge and oil sludge modification agents diluted with water and the mixture was stirred to prepare a mixture of modified oil sludge;

[0013] b •将石油焦、分散剂及步骤a制备的改性含油污泥混合液加入磨机中磨制,使固体颗粒粒径<〇.5ram从而获得所述含油污泥水焦浆。 [0013] b • modifying the oily sludge petroleum coke, a dispersing agent was added a mixed solution prepared in step a grinding mill, the solid particle size <〇.5ram water so as to obtain the oily sludge coke slurry.

[0014]由上述公开的技术方案可见,本发明利用含油污泥、石油焦制备含油污泥水焦浆, 充分利用了污泥中的水分、热量。 [0014] seen from the above disclosed technical solution, the present invention utilizes sludge, petroleum coke, coke prepared aqueous slurry of oil sludge, sludge full use of water, heat. 本发明操作简单,耗能少,成本低,产生的二次污染少。 The present invention is simple, less energy consumption, low cost, and less secondary pollution generated. 该制备方法具有改善水焦浆的流变性与稳定性的优点。 This preparation method has the advantage of improved rheology and stability of the aqueous slurry of coke. 所获得水焦浆为屈服假塑性流体,长时间放置不会产生硬沉淀,并且流动性好,适合栗送,可以作为燃料燃烧或气化原料。 The obtained aqueous slurry of coke yield pseudoplastic fluid, place a long time will not produce a hard precipitate, and good fluidity, suitable for sending Li, can be used as fuel combustion or gasification feedstock.

[0015] 本发明的含油污泥水焦浆,不仅可燃组分高,且可提高水焦浆的挥发分提高水焦浆的可燃性。 [0015] Oily sludge coke water slurry of the present invention, not only the high combustible component, and can improve water-volatile coke slurry water partial enhance the combustibility of coke slurry. 含油污泥中含有的大量铁、镍等组分,可以提高石油焦的反应活性,从而提高石油焦的利用效率。 A lot of iron, nickel and the like contained in the oily sludge components, the reactivity of petroleum coke can be improved, thereby enhancing the utilization efficiency of the petroleum coke.

[0016] 本发明制备的高浓度含油污泥水焦浆可以作为燃料燃烧,或气化原料。 High concentrations of oily sludge coke water slurry preparation of the present invention [0016] This can be burned as fuel or gasified starting material. 不仅充分利用含油污泥中的热值,而且还克服了含油污泥水分高、热处理耗能高的缺点。 Only make full use of the calorific value of oil sludge, but also to overcome the oily sludge of high water content, high heat energy disadvantage. 通过高温作用有效破坏含油污泥中的有毒、有害有机污染物,客服现有工艺有毒尾气与废水排放的弊端,获得经济与环境双重效益。 By high temperature is effective to destroy the toxic oil sludge, hazardous organic pollutants, the drawbacks of prior art call toxic exhaust emissions and waste water, to obtain a double economic and environmental benefits.

附图说明 BRIEF DESCRIPTION

[0017] 图1是本发明制备含油污泥水焦浆的工艺流程示意图 [0017] FIG. 1 is a schematic view showing a process flow of oil sludge coke water slurry of the present invention

具体实施方式 Detailed ways

[0018] 实施例1 [0018] Example 1

[0019] 1.原料 [0019] 1. Materials

[0020] (1)某炼油厂含油污泥,含水量为59.9wt% ; [0020] (1) a refinery sludge, a water content of 59.9wt%;

[0021] (2)某炼油厂石油焦,含硫量为4.88wt%,灰分为0• 15wt% ; [0021] (2) petroleum coke in a refinery, a sulfur content of 4.88wt%, an ash content of 0 • 15wt%;

[0022] ⑶分散剂(萘磺酸钠甲醛缩合物); [0022] ⑶ dispersing agent (sodium naphthalene sulfonate formaldehyde condensates);

[0023] ⑷污泥改性药剂(硫酸铁); [0023] ⑷ sludge modification agents (ferric sulfate);

[0024] ⑸水。 [0024] ⑸ water.

[0025] 2.制备条件 [0025] 2. Preparation Conditions

[0026] (1)原料配比(质量百分数) [0026] (1) raw material ratio (mass percent)

[0027] 石油焦67.65 %,含油污泥3 •洲%,水28 • 53 %份,分散剂0 • 34 %份,污泥改性药剂0.1%份。 [0027] 67.65% petroleum coke, oil sludge 3 • Island%, 28 • 53% parts water, 0 • 34% parts of a dispersing agent, 0.1% sludge modification agents parts.

[0028] (2)制备方法 [0028] (2) Preparation

[0029] 首先将含油污泥与污泥改性药剂混合,并搅拌均勾,得到改性污泥。 [0029] First, the modified sludge mixed with oily sludge agents, and the hook are stirred, to obtain the modified sludge. 将石油焦、水及分散剂研磨混合,得到水焦浆。 The petroleum coke grinding and mixing water, and a dispersant, to obtain an aqueous slurry coke.

[0030] 3.产品性能指标 [0030] 3. Product Performance

[0031] ①外观形状:黑色浆体。 [0031] ① external shape: black slurry. 25°C下,表观粘度为1099mPa • s,有良[0032] 好的流动性,可栗送; At 25 ° C, an apparent viscosity of 1099mPa • s, have good [0032] good flowability, Li sent;

[0033] ②固含率(质量%):69%; [0033] ② solid content ratio (mass%): 69%;

[0034] ③浆体中固体颗粒粒径:小于500微米; [0034] ③ slurry of solid particle size: less than 500 microns;

[0035] ④稳定性:8天不出现软沉淀,12天不出现硬沉淀。 [0035] ④ Stability: 8 days no precipitation occurs soft, hard precipitation does not occur 12 days.

[0036] 实施例2 [0036] Example 2

[0037] 1.原料 [0037] 1. Materials

[0038] 同实施例1 [0038] Example 1 with

[0039] 2.制备条件 [0039] 2. Preparation Conditions

[0040] (1)原料配比(质量百分数) [0040] (1) raw material ratio (mass percent)

[0041] 石油焦65 • 39 %,含油污泥6 • 54%,水27 • 54 %份,分散剂0 • 33%份,污泥改性药剂0.20%份。 [0041] Petroleum coke 65 • 39%, oily sludge 6 • 54%, 27 • 54% parts water, 0 • 33% parts of a dispersant, sludge modification agents 0.20% parts.

[0042] (2)制备方法 [0042] (2) Preparation

[0043] 同实施例1 [0043] Example 1 with

[0044] 3.广品性能指标 [0044] 3. The wide product performance

[0045] ①外观形状:黑色浆体。 [0045] ① external shape: black slurry. 25°C下,表观粘度为l〇63mPa • s,有良好的流动性,可泵送; At 25 ° C, an apparent viscosity of l〇63mPa • s, with good flowability, pumpable;

[0046] ②固含率(质量%) :68%; [0046] ② solid content ratio (mass%): 68%;

[0047] ③浆体中固体颗粒粒径:小于500微米; [0047] ③ slurry of solid particle size: less than 500 microns;

[0048] ④稳定性:15天不出现硬沉淀。 [0048] ④ Stability: 15 days no precipitation occurred hard.

Claims (1)

1.一种含油污泥水焦浆,其特征在于:以质量100%计,由以下各组分组成:石油焦67.65% ;含油污泥3.38% ;分散剂0 • 34% ;含油污泥改性药剂〇• 1 % ;余量为水;所得到的含油污泥水焦浆的固含量为69%;或者, _ 以质量100%计,由以下各组分组成:石油焦65.39% ;含油污泥6.54% ;分散剂0 • 33 % ; 含油污泥改性药剂0.2% ;余量为水;所得到的含油污泥水焦浆的固含量为68% ; 其中, 所述的分散剂为萘磺酸钠甲醛缩合物; 所述的含油污泥改性药剂为硫酸铁; 所述含油污泥为原油在开采、运输、加工过程中形成的油、水混合物,或还包含有乳化剂、固体颗粒、无机盐在内的一种或几种,其含水量为59 • 9% ; 所述石油焦的含硫量为4.88%,灰分为〇• 15% ; 所述的含油污泥水焦浆是通过如下方法制备得到的: a.含油污泥与含油污泥改性药剂混合搅拌并加水稀释,制备改性含油污泥 A coke slurry oil sludge water, characterized in that: on 100% by mass, consisting of the following constituents: petroleum coke 67.65%; 3.38% oily sludge; dispersing 0 • 34%; oily sludge changed of drug square • 1%; the balance being water; solids content oily sludge coke water slurry obtained was 69%; alternatively, _ 100% by mass, consists of the following components: 65.39% petroleum coke; oil sludge 6.54%; dispersant 0 • 33%; oily sludge modification agents 0.2%; the balance being water; solids content oily sludge coke water slurry obtained was 68%; wherein said dispersant is sodium naphthalene sulfonate formaldehyde condensate; oil sludge modification agents according to ferric sulfate; the oleaginous crude oil sludge formation in the mining, transportation, processing, water, or a mixture further comprises an emulsifier, solid particles, including one or more inorganic salts, a water content of 59 • 9%; sulfur content of the petroleum coke is 4.88%, ash square • 15%; oily sludge according to water power slurry was prepared by the following method:. a oily sludge and oil sludge modification agents were mixed and stirred and diluted with water to prepare a modified oil sludge 合液; b •将石油焦、分散剂及改性含油污泥混合液加入磨机中磨制,使固体颗粒粒径< 0.5mm〇 Prepared solution; b • petroleum coke, oil sludge dispersant and modifiers added to the mixture in the grinding mill, the solid particle size <0.5mm〇
CN201210184886.0A 2012-06-06 2012-06-06 OILY water sludge coke slurry and preparation method CN103468333B (en)

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