CN103408392A - Polyvinyl chloride loop route production method - Google Patents
Polyvinyl chloride loop route production method Download PDFInfo
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- CN103408392A CN103408392A CN2013103008424A CN201310300842A CN103408392A CN 103408392 A CN103408392 A CN 103408392A CN 2013103008424 A CN2013103008424 A CN 2013103008424A CN 201310300842 A CN201310300842 A CN 201310300842A CN 103408392 A CN103408392 A CN 103408392A
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- calcium carbide
- polyvinyl chloride
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- ethylene dichloride
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a polyvinyl chloride loop route production method (short for loop route method), and belongs to the field of new coal chemical industry materials and the technical field of polymer material science and engineering, and relates to a polyvinyl chloride green production technology with characteristics of high efficiency, energy saving, and environmental protection. According to the method, actual production starts from an oxygen-rich calcium carbide high temperature reaction furnace, oxygen-rich calcium carbide reacts in the high temperature reaction furnace to obtain a solid product calcium carbide and synthesis gas carbon monoxide, the subsequent process is divided into two branches, one branch process is preparing acetylene from the calcium carbide, the other branch process is preparing ethanol from the synthesis gas carbon monoxide, and then preparing dichloroethane through ethanol chlorination, a closed loop is formed after the two branch reactions are completed and combined, both end products acetylene and dichloroethane can be subjected to a reaction by using a mercury-free catalyst to prepare a vinyl chloride monomer, and the existing technology can be adopted to prepare the PVC from the vinyl chloride monomer. According to the present invention, the reacting calcium carbide residue can be used for producing cement, and the synthesis gas CO can completely participate in the subsequent reactions so as to achieve zero emission; and the expansion loop method can be adopted to achieve multi-function and multi-efficacy co-production operation.
Description
Technical field
The present invention relates to a kind of environmental protection, energy-conservation, efficient polyvinyl chloride annular synthetic route Green production method.Belong to Coal Chemical Industry field of new and polymer material science and field of engineering technology.
Background technology
Polyvinyl chloride (hereinafter to be referred as PVC) is the kind of consumption maximum in five large resins for universal use, is widely used in the numerous areas such as building, automobile, high ferro, boats and ships, aerospace and defence and military, in national economy and social development, has very important status.The building materials of take are example, and PVC compares with traditional material, all more energy-conservation in production and use procedure, and therefore, the PVC door and window is universal already in European and American developed countries, and China also classifies it as the chemical building material that keypoint recommendation is used.Existing PVC starting material production technique mainly contains two kinds of ethylene process and calcium carbide routes.Whole world overwhelming majority of countries all adopts the ethylene process route.China is due to the resource structures characteristics of " oil starvation, weak breath, rich coal ", makes ethylene process route Arrested Development and mainly takes calcium carbide route (carbide acetylene) route.At present, the PVC of employing carbide acetylene raw material production accounts for 80% left and right of ultimate production.The relative merits of these two kinds of traditional technology routes are summarized as follows respectively:
The calcium carbide process PVC operational path be take coal, Wingdale and hydrogenchloride and is raw material.Coke reacts and makes calcium carbide at high-temperature molten-state with Wingdale, and calcium carbide reacts with water and generates acetylene gas, and acetylene and hydrogenchloride addition reaction generate vinylchlorid (VCM), and last polymerization obtains PVC, and its technical process as shown in Figure 1.As everyone knows, the calcium carbide production energy consumption is high.Simultaneously, calcium carbide process PVC is produced the VCM monomer need to be with mercuric chloride catalyst as catalyzer, and PVC per ton consumes mercury catalyst 1.2kg, produces 1,000 ten thousand tons and will consume 1.2 ten thousand tons of catalyst, uses 1320 tons, mercury chloride.Therefore, this route exists highly energy-consuming, the dual problem of high pollution.
Ethylene process PVC operational path is to be raw material with ethene, iron trichloride commonly used is catalyzer, ethene and chlorine carry out gas phase or liquid phase reaction generates ethylene dichloride, ethylene dichloride cracking in pyrolyzer generates vinylchlorid and hydrogenchloride, wherein hydrogenchloride reuse, with ethene and oxygen reaction, generate ethylene dichloride again, and chloroethylene polymerization generates PVC, the method is called process for oxychlorination of ethylene.This is current most widely used PVC production method in the world, and its technical process is shown in as shown in Figure 2.Ethylene process is produced PVC and is polluted less, consume energy low, but it must rely on petroleum resources, and facility investment is large, and production cost is high.
Summary of the invention
The object of the present invention is to provide a kind of environmental protection, energy-conservation, efficient PVC production method, particularly for not relying on petroleum resources, and prepare PVC based on Wingdale rich in mineral resources, and solve the problem of existing calcium carbide route mercury pollution and highly energy-consuming, realize the green production of environmental protection and energy saving.
The technical scheme adopted for achieving the above object is: polyvinyl chloride circuit production method, be called for short " loop method " PVC technique, as shown in Figure 3, wherein double-lined arrow is depicted as the main technique route to flow process, and it is closed-loop structure and can has a style of one's own and formed technique.
The open loop mode of loop method technique of the present invention and aforementioned calcium carbide route or ethene is completely different, actual production is the high temperature reaction stove from the oxygen enrichment calcium carbide, Wingdale+raw material of wood-charcoal+oxygen is as the raw material of oxygen enrichment calcium carbide, the oxygen enrichment calcium carbide obtains solid resultant calcium carbide and synthetic gas CO in the pyroreaction reaction in furnace, technique subsequently is divided into two branches, and one (extending left in Fig. 3) can make acetylene by calcium carbide; Another (extending to the right in Fig. 3) can first make ethanol from synthetic gas CO, then makes ethylene dichloride by the ethanol chlorination; After two branches (two techniques in left and right in Fig. 3) reaction, converge the formation closed loop, two ends product acetylene reacts with ethylene dichloride and can make vinyl chloride monomer (VCM), adopts prior art can obtain PVC by VCM again.
In polyvinyl chloride circuit production method technique of the present invention, from synthetic gas CO to ethylene dichloride, many routes can be arranged: both can be from synthetic gas CO through the ethanol link to ethylene dichloride, also can be through by methanol-to-olefins method (MTO) synthesizing ethylene, arriving again ethylene dichloride.
Polyvinyl chloride circuit production method technique of the present invention can also be according to actual needs at each productive unit, from outside, obtains or product that postreaction is required, or provide intermediate product to outside.
Polyvinyl chloride circuit production method of the present invention and the contrast of traditional calcium carbide route, reaction process can be adopted without mercury catalyst as new catalyst, because being catalyst without mercury, thereby have thoroughly solved the mercury pollution environmental issue that the vinylchlorid industry faces
Effect of the present invention:
1); Polyvinyl chloride circuit production method of the present invention and the contrast of traditional calcium carbide route, namely have the advantage of abundant raw material can avoid using again mercury catalyst, adopts without mercury catalyst as new catalyst, thereby thoroughly solved the mercury pollution environmental issue that the vinylchlorid industry faces
2) loop method of the present invention is compared with ethylene process, with being arranged, environment-friendly advantage avoided the dependence for petroleum resources, in addition, the method has only retained the simplest of ethylene process Unit three, it is ethylene chlorination ethylene dichloride processed, and saved ethylene dichloride cracking unit and the complicated oxychlorination unit of equipment of high energy consumption, have a facility investment few, the two-fold advantage that production energy consumption is low;
3) loop method of the present invention is taked technique closed loop route, after smelting furnace lower end (in Fig. 3 extension process) left solid resultant calcium carbide prepared acetylene, remaining carbide slag can be used for producing cement, smelting furnace upper end (in Fig. 3 extension process) to the right synthetic gas CO all participates in subsequent reactions, not only realize zero release, and the flow process shortening, heat absorption and thermopositive reaction coupling, thereby decrease production energy consumption, compared with prior art, has environmental protection and energy saving effect significantly;
4) loop method of the present invention is green production process, simultaneously, can also according to actual needs, from outside, obtain or provide intermediate product to outside at each productive unit.For example, the bio-ethanol the ethanol link can receive outside to provide, obtain equivalent acetylene raw material in the acetylene link by methods such as sky hot gas or coal plasma bodys, thereby realize multi-functional, multi-effect coproduction operation.
The accompanying drawing explanation
Fig. 1 is the calcium carbide process PVC technological process of production (open loop) schematic diagram.
Fig. 2 is the ethylene process PVC technological process of production (open loop) schematic diagram.
Fig. 3 is the polyvinyl chloride circuit production method technological process of production of the present invention (closed loop) schematic diagram.
Fig. 4 is polyvinyl chloride circuit production method of the present invention, an embodiment fundamental cycle method PVC production technological process.
Fig. 5 is polyvinyl chloride circuit production method of the present invention, and an embodiment expands loop method PVC production technological process.
Embodiment:
Embodiment mono-, fundamental cycle method PVC production technique
As shown in Figure 4, production technique and equipment embodiment are as follows for the basic loop method technical process of the polyvinyl chloride of the present embodiment:
1) initial: the oxygen enrichment furnace of calcium carbide adopts shaft furnace, adopt raw materials pretreatment compounding device to prepare limestone powder and coal dust, to delivering and have the limestone powder of strict ratio requirement and the uniform mixture of coal dust in stove, under the Optimizing Technical of setting, carry out stable reacting with oxygen, synthetic gas CO is derived on top, calcium carbide is derived in bottom, as shown in Figure 4, from the left and right sides, enters respectively next step flow process.
2) left road: from deriving calcium carbide the shaft furnace reactant, adopt the UTILIZATION OF VESIDUAL HEAT IN efficiency acetylene generator, calcium carbide being reacted with water and produce acetylene is next step response preparation raw material, simultaneously waste heat is taken full advantage of, and utilizes conveying and finishing apparatus that carbide slag is converted into to material of construction.
3) right wing: under the condition that the waste heat of the synthetic gas carbon monoxide that the shaft furnace upper end is derived takes full advantage of, reaction obtains ethanol, then by preparing ethylene by dehydrating ethanol, then by ethylene chlorination, prepare the raw material of ethylene dichloride (also can directly prepare ethylene dichloride by the ethanol chlorination) as next step reaction.
4) join: acetylene prepared by employing prior art Jiang Zuo road reacts and prepares vinyl chloride monomer with ethylene dichloride prepared by right wing, import in polymeric kettle and carry out polyreaction and obtain the PVC suspended substance, through separating drying plant, obtain the PVC powder, the recycling present device realizes in PVC polymer melt mould or the outer nano-stack infinitesimal analysis mixing facilities granulation of mould, the PVC coacervate is fully launched, obtain the PVC product of high-performance and high added value.
In said process, adopt without mercury catalyst as catalyzer, such as: active substance with the muriate of tin chloride, rare earth and other precious metal etc.
Embodiment bis-, expansion loop method PVC production technique
The polyvinyl chloride expansion hula route of the present embodiment, in order to use the diversity of country variant and regions resources structure, basic circuit middle-chain open window is set, accept adding of outside intermediate raw material, be illustrated in figure 5 a concrete feasible program:
In above-mentioned shown in Figure 4 basic annular technical process the ，Dang Zuo road acetylene can be obtained supplementing by the natural gas source facility time, right wing can carry out by the bio-ethanol of natural resource supporting supplementing.
In addition, in loop method PVC green production process flow process as shown in Figure 3, if opening, any one position in Closed loop becomes open loop technique, can become a kind of feasible production technique, two kinds of current technology illustrated in figures 1 and 2 can be regarded in technique ring of the present invention the open loop operational path that removes some unit and form as.In the broadest sense, having calcium carbide and ethylene process now is also the broken specific embodiment that lacks state of the present invention's annular technique.
Claims (5)
1. polyvinyl chloride circuit production method, it is characterized in that: actual production is the high temperature reaction stove from the oxygen enrichment calcium carbide, Wingdale+raw material of wood-charcoal+oxygen is as the raw material of oxygen enrichment calcium carbide, the oxygen enrichment calcium carbide obtains solid resultant calcium carbide and synthetic gas carbon monoxide in the pyroreaction reaction in furnace, technique subsequently is divided into two branches, and one can make acetylene by calcium carbide; Another can first make ethanol from the synthetic gas carbon monoxide, then makes ethylene dichloride by the ethanol chlorination; After two branching reactions, converge the formation closed loop, two ends product acetylene reacts and can make vinyl chloride monomer with ethylene dichloride, adopts prior art can obtain PVC by vinyl chloride monomer again.
2. polyvinyl chloride circuit production method according to claim 1, it is characterized in that: reaction process can adopt without mercury catalyst.
3. polyvinyl chloride circuit production method according to claim 1 is characterized in that: can be from synthetic gas CO from synthetic gas CO to ethylene dichloride through the ethanol link to ethylene dichloride, or can be through by MTO method synthesizing ethylene, arriving again ethylene dichloride.
4. polyvinyl chloride circuit production method according to claim 1, it is characterized in that: after smelting furnace lower end solid resultant calcium carbide prepared acetylene, remaining carbide slag can be used for producing cement.
5. polyvinyl chloride circuit production method according to claim 1, is characterized in that: at the product that each productive unit can also obtain from outside or postreaction is required, or provide intermediate product to outside.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408393A (en) * | 2013-07-17 | 2013-11-27 | 北京化工大学 | Polyvinyl chloride loop route production method |
| CN104448073A (en) * | 2014-11-14 | 2015-03-25 | 清华大学 | Polyvinyl chloride production process dispatching method |
| CN107311835A (en) * | 2017-06-02 | 2017-11-03 | 青海盐湖工业股份有限公司 | The processing system and processing method of rectifying height boiling raffinate in a kind of carbide production vinyl chloride |
| US11180371B2 (en) | 2019-04-12 | 2021-11-23 | J. Dustin Hultine | Integrated synthesis of commodity chemicals from waste plastic |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408393A (en) * | 2013-07-17 | 2013-11-27 | 北京化工大学 | Polyvinyl chloride loop route production method |
| US9783629B2 (en) | 2013-07-17 | 2017-10-10 | Beijing University Of Chemical Technology | Loop-route production method and system for polyvinyl chloride |
| CN104448073A (en) * | 2014-11-14 | 2015-03-25 | 清华大学 | Polyvinyl chloride production process dispatching method |
| CN107311835A (en) * | 2017-06-02 | 2017-11-03 | 青海盐湖工业股份有限公司 | The processing system and processing method of rectifying height boiling raffinate in a kind of carbide production vinyl chloride |
| CN107311835B (en) * | 2017-06-02 | 2020-10-27 | 青海盐湖工业股份有限公司 | Treatment system and treatment method for rectifying high-boiling residual liquid in production of chloroethylene by calcium carbide method |
| US11180371B2 (en) | 2019-04-12 | 2021-11-23 | J. Dustin Hultine | Integrated synthesis of commodity chemicals from waste plastic |
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Application publication date: 20131127 |