CN104418696A

CN104418696A - Method for synthesizing PVC (Polyvinyl Chloride) or vinyl acetate by taking CO or methanol as raw material

Info

Publication number: CN104418696A
Application number: CN201310407564.2A
Authority: CN
Inventors: 李坚
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-08-31
Filing date: 2013-08-31
Publication date: 2015-03-18

Abstract

The invention relates to a method for synthesizing PVC (Polyvinyl Chloride) or vinyl acetate by taking carbon monoxide (CO) or methanol as a raw material. At present, according to the method for synthesizing PVC or vinyl acetate all over the world, carbide acetylene or petro-ethylene is taken as a raw material, and any literature or report of any information related to a route of synthesizing PVC or vinyl acetate by taking CO or methanol as the raw material is absent. Compared with the traditional synthetic route, the synthetic route disclosed by the invention has the advantages that the production cost is reduced by over 10-20 percent, and the emission amount of carbide-slag slurry is reduced by 100 percent.

Description

With CO or methyl alcohol as Material synthesis PVC or vinyl acetate between to for plastic

One, technical field

The present invention relates to a kind of with carbon monoxide or methyl alcohol be Material synthesis PVC (polyvinyl chloride) or vinyl acetate between to for plastic method and purposes, at present, the method of whole world synthesizing polyvinyl chloride or vinyl acetate between to for plastic is all adopt carbide acetylene or oil ethene to be raw material, yet there are no the report of the even any information of any document of the route adopting CO or methyl alcohol as Material synthesis PVC or vinyl acetate between to for plastic, synthetic route of the present invention is compared with conventional synthesis route, decline production cost more than 10 ~ 20%, reduces carbide slag slurries quantity discharged 100%.

Two, background technology

Carbon monoxide molecule formula is CO, and methanol molecules formula is CH ₃oH, the Chemicals that their two of belonging to that coal chemical technology knows the most are basic, polyvinyl chloride (PVC) is the normally used a kind of plastic material of people, global annual production has risen to more than 4,500 ten thousand tons, the annual production of vinyl acetate between to for plastic has also risen to more than 1,000 ten thousand tons, and, they year consumption still with 3 ~ 5% speed increase.Traditional production process route is mainly carbide acetylene method or oil ethylene process, there is high, the heavy-polluted defect of cost in carbide acetylene method, more and more can not adapt to the requirement of Sustainable development, such as: China Chemical Industry report is reported, from 2012, the enterprise of the calcium carbide route production polyvinyl chloride of China faced whole industry loss; Oil ethene normal is along with the continuous increase of petroleum-based energy crisis; clearly; the method will be eliminated in 20 years from now on; but; plastic material will become the indispensable articles for use of human society for a long time; for this reason, people are making great efforts the technology developing coal ethene and acetylene always, attempt to replace above-mentioned carbide acetylene method and oil ethylene process as early as possible.

The professional technique work of the present inventor's long campaigns chemical pharmacy field, has found " CO 2012 Christian eras ₂, CO deoxidation self-coupling reaction " this brand-new building-up reactions pattern; and by a large amount of small test; demonstrate the most excellent raw material that carbon monoxide or carbonic acid gas belong to nearly all c2 compounds such as synthesis acetylene, ethene, ethanol, ethylene glycol, acetic acid, ethane, acetaldehyde, construct carbon monoxide of the present invention or the methyl alcohol method and uses thereof as Material synthesis polyvinyl chloride or vinyl acetate between to for plastic thus.

In inorganic chemistry, CO and CO ₂all belong to typical carbonyl compound, at chemical pharmacy field, we often use carbonyl reduction linked reaction to build new C-C key organism, wherein classical reaction pattern has write from memory auspicious coupling, acyloin coupling, frequently alcohol coupling, the coupling of amber gold, gram slave that lids more than one all of Mike receiving coupling, Shi Tuobei coupling, Wittig coupling, these linked reactions are generally all carried out under the condition of the gentleness of normal temperature, normal pressure, but surprisingly, the present inventor studies nearly thousand sections carefully about with CO or CO ₂for the organic document of Material synthesis, do not find that there is one section of document and relate to CO or CO ₂autoimmunity syndrome reaction, almost all specification, in the type of the addition reaction of carbonyl, in fact, as long as analyze from the principle of above-mentioned classical linked reaction, just can find CO or CO ₂molecular weight little, spatial obstacle is little, and CO is metastable carbonyl, CO ₂be two superimposed carbonyls, these two kinds of carbonyls all belong to more active carbonyl, and they should have the reactive behavior of higher reductive coupling, the substrate of the reaction such as auspicious coupling and alcohol coupling frequently that is highly suitable for writing from memory as Mike, especially CO or CO ₂not containing H atom in molecule, the competing reaction of acyloin coupling, aldol condensation, the reaction of this class of Kang Nizhaluo can not be there is, so derive in theory, CO or CO ₂the raw material that in carbonyl compound, linked reaction selectivity is the most excellent should be belonged to, or perhaps the most excellent raw material of synthesis two carbon organic combounds.Method of the present invention, has used the principle of carbonyl reduction linked reaction just, and creating with CO and water or methyl alcohol is the full technical strategies of Material synthesis acetylene, compared with preparing acetylene, has following several feature with calcium carbide route:

A, be that acetylene prepared by raw material with CO and water or methyl alcohol, whole production process is without the discharge of waste gas, waste water, waste residue, and be the industrial effluent that raw material production 1 ton of acetylene generates 10 tons of solid contents about 12% simultaneously with calcium carbide, be commonly called as carbide slag slurries, often produce 1 ton of PVC product by calcium carbide route, discharge carbide slag slurries about 20 tons;

The production cost of b, calcium carbide is 1.5 times of CO, produces 1 ton of acetylene and consumes 2.5 tons, calcium carbide, is be more than 2 times of the cost of raw material production acetylene with CO with the cost of calcium carbide method acetylene production;

C, be that acetylene prepared by raw material with carbon monoxide and water or methyl alcohol, processing condition as mild as a dove, normal temperature, normal pressure, single stage method, and without the need to selecting special catalyzer, nearly all metal simple-substance and alloy thereof or non-metal simple-substance can effectively use as catalyzer, also without the need to designing special reactor, can adopt conventional interval type or flow reactor.

Above-mentioned CO synthesizes the route of acetylene, it is take CO as carbon source that principle belongs to, water or methyl alcohol are hydrogen source, under the chemical environmental conditions of low temperature, highly basic, be the carbonyl reduction linked reaction that catalyzer carries out with metal simple-substance, by adjusting process condition and catalyzer, while easy generation acetylene, further hydrogenating reduction generates ethene or ethane, so, synthetic route of the present invention can be referred to as with CO or the methyl alcohol route as Material synthesis acetylene or ethene, compared with the route preparing ethene with traditional oil, production cost declines more than 1 times.

Synthetic route metal simple-substance of the present invention is catalyzer, the corresponding metal hydroxides of easy by-product, increase preparation cost thus, this problem is resolved by another invention about aluminium hydroxide one-step synthesis method aluminium simple substance of the present inventor (be the patent of invention of 201310084785.0 see application number).In summary, using carbon monoxide of the present invention or the methyl alcohol method as Material synthesis acetylene or ethene, be applied to synthesizing polyvinyl chloride or vinyl acetate between to for plastic, compare existing carbide acetylene method and oil ethylene process, not only reduce the production cost 10 ~ 20% of PVC or vinyl acetate between to for plastic, and reduce calcium carbide waste slag quantity discharged 100%.

Three, summary of the invention

The object of this invention is to provide method and carbon monoxide thereof that a kind of carbon monoxide or methyl alcohol are Material synthesis polyvinyl chloride or vinyl acetate between to for plastic or the methyl alcohol purposes as the raw material of synthesizing polyvinyl chloride or vinyl acetate between to for plastic, content of the present invention is exactly take CO as carbon source, water or methyl alcohol are hydrogen source, in conjunction with method and the principle of metal and water hydrogen manufacturing, replace traditional method of calcium carbide acetylene or oil ethene, be applied to the manufacturing enterprise of existing acetylene method or ethylene process synthesis PVC or vinyl acetate between to for plastic, the effect reducing production cost significantly and reduce environmental pollution can be reached.

1, by carbon monoxide and the water method as Material synthesis acetylene or ethene, several steps of following order are comprised:

1.1 synthesis acetylene

Select conventional interval type or flow reactor, drop into all alkaline aqueous solution such as the potassium hydroxide of 30% of calculated amount or the tetra-alkyl ammonium hydroxide aqueous solution of sodium hydroxide or lithium hydroxide aqueous solution or input 25% in reactor, the iron of input or load calculated amount again, copper, plumbous, tin, nickel, zinc, all metal simple-substances such as manganese or its alloy are in this reactor, control temperature less than 40 DEG C, pressure is normal pressure or low pressure, slowly pass into the CO of calculated amount or the synthetic gas of routine from reactor bottom, retain certain reaction times, from reactor head out be exactly acetylene gas.

1.2 synthesizing ethylene

Select conventional interval type or flow reactor, drop into all alkaline aqueous solution such as the potassium hydroxide of 30% of calculated amount or the tetra-alkyl ammonium hydroxide aqueous solution of sodium hydroxide or lithium hydroxide aqueous solution or input 25% in reactor, the aluminium of input or load calculated amount again, zinc, plumbous, germanium, beryllium, all amphoteric element simple substance such as silicon and alloy thereof are in this reactor, control temperature less than 80 DEG C, pressure is normal pressure or low pressure, slowly pass into the CO of calculated amount or the synthetic gas of routine from reactor bottom, retain certain reaction times, from reactor head out be exactly ethylene gas.

2, carbon monoxide and methyl alcohol are as the method for Material synthesis acetylene or ethene, comprise several steps of following order:

2.1 synthesis acetylene

Select conventional interval type or flow reactor, drop into calculated amount 25% tetra-alkyl ammonium hydroxide methanol solution or 25% sodium methoxide solution in reactor, drop into again all metal simple-substances such as the iron of calculated amount, copper, lead, tin, nickel, zinc, manganese and alloy thereof in this reactor, control temperature less than 40 DEG C, pressure is normal pressure, low pressure, slowly pass into the CO gas of calculated amount or the synthetic gas of routine from reactor bottom, retain certain reaction times, from reactor head out be exactly acetylene gas.

2.2 synthesizing ethylene

Select conventional interval type or flow reactor, drop into calculated amount 25% tetra-alkyl ammonium hydroxide methanol solution or 25% sodium methoxide solution in reactor, drop into again or all amphoteric element simple substance such as aluminium, zinc, germanium, beryllium, silicon of load calculated amount and alloy thereof in this reactor, control temperature less than 60 DEG C, pressure is normal pressure, low pressure, the CO gas of calculated amount or the synthetic gas of routine is passed into from reactor bottom, retain certain reaction times, from reactor head out be exactly ethylene gas.

3, use methyl alcohol as the method for Material synthesis ethene, comprise several steps of following order:

Select conventional interval type or flow reactor, drop into calculated amount 25% tetra-alkyl ammonium hydroxide methanol solution or 25% sodium methoxide solution in reactor, drop into again or all amphoteric element simple substance such as beryllium, germanium, zinc, lead, tin, silicon, aluminium of load calculated amount and alloy thereof in this reactor, control temperature less than 70 DEG C, pressure is normal pressure, low pressure, retain certain reaction times, from reactor head out be exactly ethylene gas.

The method, compared with traditional preparing light olefins from methanol technique, has two features: one be method temperature of reaction of the present invention below 70 DEG C, be liquid phase reaction, and traditional technology require temperature of reaction more than 450 DEG C, be gas-phase reaction; Two are selectivity of the gaseous product of method synthesizing ethylene of the present invention is 100%, generate without propylene product, and the selectivity of traditional technology synthesizing ethylene is less than 45%, the propylene product of equivalent is had to generate, the technical characteristic of Methanol ethene of the present invention is low temperature, base catalysis, liquid phase reaction, and the technical characteristic of traditional technology is high temperature, acid catalysis, gas-phase reaction, the preparation cost of this technique declines more than 20% than the preparation cost of traditional technology.

Acetylene or ethene are the main raw materials preparing polyvinyl chloride or vinyl acetate between to for plastic, general calcium carbide route prepares the manufacturing enterprise of PVC or vinyl acetate between to for plastic, need to have the workshop that calcium carbide produces acetylene, general ethylene process prepares the manufacturing enterprise of PVC or vinyl acetate between to for plastic, need to lay long-distance pipe for carrying ethylene gas, but adopt CO of the present invention or methyl alcohol as the method for Material synthesis acetylene or ethene, the production plant of calcium carbide ethene and the long-distance pipe of conveying ethene can be saved completely, can directly adopt the CO or methyl alcohol or synthetic gas that produce voluntarily as the raw material synthesizing PVC or vinyl acetate between to for plastic, create the new cleanproduction process that CO of the present invention or methyl alcohol are Material synthesis PVC or vinyl acetate between to for plastic thus.

Four, embodiment

Embodiment 1

Select conventional stainless steel stirred reactor (volume 1L) to drop into potassium hydroxide or sodium hydroxide or lithium hydroxide aqueous solution 400 ~ 600 grams that content is more than 30%, drop into content be more than 25% Tetramethylammonium hydroxide or the tetraethyl ammonium hydroxide aqueous solution 400 ~ 600 grams in reactor, start and stir, slowly add the zinc particle of 20 ~ 80 grams or zinc powder or the amphoteric metal such as lead powder or glass putty, control temperature 20 ~ 40 DEG C, pressure is 0 ~ 0.5MPa, the CO gas of 15 ~ 30 gram 99% is slowly passed into from reactor bottom, insulation reaction 1 ~ 5 hour, the gas collecting reactor head is acetylene, CO transformation efficiency is 99%, acetylene yield is more than 95%.

Embodiment 2

Select conventional stainless steel stirred reactor (1L), drop into sodium hydroxide or potassium hydroxide or lithium hydroxide aqueous solution 400 ~ 600 grams that content is more than 30%, drop into content be more than 25% Tetramethylammonium hydroxide or the tetraethyl ammonium hydroxide aqueous solution 400 ~ 600 grams in reactor, drop into again the copper powder of 20 ~ 80 grams or reduced iron powder or nickel powder or manganese powder etc. all can the non-amphoteric metal simple substance of deoxidation and alloy thereof in this reactor, start and stir, control temperature 60 ~ 80 DEG C, pressure is 0 ~ 0.5MPa, the CO gas 15 ~ 30 grams of 99% is slowly passed into from reactor bottom, insulation reaction 6 ~ 12 hours, the gas collecting reactor head is acetylene, CO transformation efficiency is 99%, acetylene yield is more than 95%.

Embodiment 3

Select conventional stainless steel stirred reactor (1L), drop into content be more than 30% sodium hydroxide potassium hydroxide or lithium hydroxide aqueous solution 400 ~ 600 grams or drop into content be more than 25% Tetramethylammonium hydroxide or the tetraethyl ammonium hydroxide aqueous solution 400 ~ 600 grams in reactor, drop into again activated carbon loaded copper or iron or nickel or manganese simple substance 60 ~ 100 grams in this reactor, start and stir, control temperature 80 DEG C, pressure is 0 ~ 0.5MPa, conventional synthetic gas 30 ~ 60 grams is slowly passed into from reactor bottom, insulation reaction 14 hours, the gas collecting reactor head is the gas mixture of acetylene and hydrogen, acetylene content is greater than 85%, acetylene yield is 97%.

Embodiment 4

Select conventional fixed-bed reactor, wherein load activated carbon loaded iron or copper or plumbous or tin or nickel or zinc etc. all can be oxidized metal simple-substance or its alloy, with pump by content be more than 30% sodium hydroxide or potassium hydroxide or lithium hydroxide aqueous solution be back to reactor head from flowing out outer circulation from reactor bottom again reactor head is drenched, control temperature 20 ~ 80 DEG C, pressure is 0 ~ 0.5MPa, the synthetic gas of pure CO gas or routine is continuously passed into from reactor bottom, constantly acetylene product is collected from reactor head, after separating-purifying, directly send into PVC or vinyl acetate synthesis workshop, acetylene yield is more than 95%.

Embodiment 5

Select conventional stainless steel stirred reactor (1L), drop into content be more than 25% tetramethyl-tetraethyl ammonium hydroxide methanol solution or drop into 25% potassium tert-butoxide solution 400 ~ 600 grams in reactor, drop into again iron powder or copper powder or zinc powder or nickel powder or lead powder or manganese powder 20 ~ 80 grams, start and stir, control temperature 20 ~ 40 DEG C, pressure is 0 ~ 0.5MPa, the CO gas 15 ~ 30 grams of 99% is slowly passed into from reactor bottom, acetylene gas is collected from reactor head, by-product methylal, CO transformation efficiency 99%, acetylene yield 97%, methylal yield 82%.

Embodiment 6

Select conventional stainless steel stirred reactor (1L), drop into potassium hydroxide or sodium hydroxide or lithium hydroxide aqueous solution 400 ~ 600 grams that content is more than 30%, drop into content be more than 25% Tetramethylammonium hydroxide or the tetraethyl ammonium hydroxide aqueous solution 400 ~ 600 grams in reactor, drop into again the aluminium powder of 40 ~ 80 grams or zinc powder in this reactor, start and stir, control temperature 40 ~ 80 DEG C, pressure is 0 ~ 0.8MPa, the pure CO of 15 ~ 30 grams or the synthetic gas of routine is slowly passed into from reactor bottom, ethylene gas is collected from reactor head, by-product ethylene dichloride, CO transformation efficiency 99%, yield of ethene 87%, ethylene dichloride yield 7%.

Embodiment 7

Select conventional stainless steel stirred reactor (volume 1L), drop into content be more than 25% Tetramethylammonium hydroxide tetraethyl-ammonium oxide methanol solution or 25% potassium tert-butoxide solution 400 ~ 600 grams in reactor, input aluminium powder or zinc powder 60 ~ 90 grams are in this reactor again, start and stir, control temperature is less than 60 DEG C, pressure is 0 ~ 0.5MPa, the CO gas of 99% or the synthetic gas 15 ~ 30 grams of routine is slowly passed into from reactor bottom, ethylene gas is collected from reactor head, by-product ethylene dichloride, yield of ethene 85%, ethylene dichloride yield 10%.

Embodiment 8

Select conventional interval type or flow reactor (1L), drop into calculated amount 25% Tetramethylammonium hydroxide tetraethyl ammonium hydroxide methanol solution or 25% methanol solution of sodium methylate 400 ~ 600 grams in reactor, drop into simple substance or activated carbon loaded beryllium again, germanium, zinc, plumbous, tin, silicon, aluminium, all amphoteric element simple substance such as manganese and alloy thereof are in this reactor, start mixing control temperature of reaction less than 70 DEG C, pressure is normal pressure, low pressure, retain certain reaction times, from reactor head out be exactly ethylene gas, ethylene selectivity 99% in gas, yield of ethene 94%.

Embodiment 9

Select the reactor of conventional acetylene method synthesizing chloroethylene, after acetylene gas above-described embodiment 1 to embodiment 5 prepared and dry HCl gas mix in input reactor, copy the processing condition of traditional synthesizing chloroethylene by acetylene to carry out the reaction of synthesizing chloroethylene completely, the once through yield of the vinylchlorid obtained is 70%.

Embodiment 10

Select the reactor of conventional ethylene process synthesizing chloroethylene, the ethene prepared by above-described embodiment 6 to embodiment 8 is as raw material, input in this reactor together with the raw materials such as oxygen, copy the processing condition of traditional ethene preparing chloroethylene to carry out the reaction of synthesizing chloroethylene completely, the total recovery of the vinylchlorid obtained is 94%.

Embodiment 11

Select the reactor of conventional VCM synthesis polyvinyl chloride, the vinylchlorid prepared by above-described embodiment 9 and embodiment 10 is as raw material, input in this reactor, copy the processing condition of traditional vinylchlorid polyvinyl chloride to carry out the reaction of synthesizing polyvinyl chloride completely, the yield of the polyvinyl chloride obtained is 92%.

Embodiment 12

Select the reactor of conventional Synthesizing Vinyl Acetate from Acetylene, with above-described embodiment 1 to embodiment 5 prepare acetylene be that raw material inputs in this reactor together with acetic acid raw material, copy the processing condition of traditional producing vinyl acetate by acetylene method to carry out building-up reactions completely, the yield obtaining vinyl acetate between to for plastic is more than 92%.

Embodiment 13

Select the reactor of conventional ethylene process synthesizing vinyl acetate, with above-described embodiment 6 to embodiment 8 prepare ethene be raw material, input in this reactor together with acetic acid and oxygen, the processing condition of copying traditional ethylene process to produce vinyl acetate between to for plastic completely carry out building-up reactions, and the yield of the vinyl acetate between to for plastic obtained is more than 92%.

Claims

1. by carbon monoxide or the methyl alcohol purposes as Material synthesis acetylene or ethene.

2., by carbon monoxide and water or the methyl alcohol method as Material synthesis acetylene or ethene, comprise several steps of following order:

Select conventional interval type or flow reactor, drop into the potassium hydroxide of calculated amount or the tetra-alkyl ammonium hydroxide aqueous solution of sodium hydroxide or lithium hydroxide aqueous solution or input 25% or methanol solution in reactor, the iron of input or load calculated amount again, copper, plumbous, tin, nickel, zinc, aluminium, germanium, all metal simple-substances such as manganese or its alloy are in this reactor, control temperature 20 ~ 80 DEG C, pressure is normal pressure or low pressure, slowly pass into the CO of calculated amount or the synthetic gas of routine from reactor bottom, retain certain reaction times, from reactor head out be exactly acetylene or ethylene gas.

3., by the method for methyl alcohol as Material synthesis ethene, its technical characteristic is low temperature, liquid phase reaction;

Highly basic and amphoteric element simple substance or the reaction of its alloy co-catalysis.

4. by carbon monoxide or the methyl alcohol purposes as Material synthesis polyvinyl chloride or vinyl acetate between to for plastic.