CN103130219A

CN103130219A - Preparing method for diamond, polycrystalline silicon, chloroform, trichlorosilane, diester carbonate, chloroformate, carbinol and methane

Info

Publication number: CN103130219A
Application number: CN201110399674XA
Authority: CN
Inventors: 李坚
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-11-28
Filing date: 2011-11-28
Publication date: 2013-06-05

Abstract

The invention relates to a universal type synthetic method based on a recent discovery of reactions of tandem substituent and rearrangement elimination (TSRE) of organic element chemistry. A production technology of diamond, polycrystalline silicon, chloroform, trichlorosilane, diester carbonate, chloroformate, carbinol and methane is redesigned. Compared with an original production technology of the products, the preparing method can solve waste water draining problems from source, and the purposes of energy conservation and emission reduction in a large-scale mode and cost lowering are achieved.

Description

The preparation method of diamond, polysilicon, chloroform and trichlorosilane, carbonic diester and chloro-formic ester, methyl alcohol and methane

The present invention relates to universal synthetic method that a kind of series connection according to organic element chemistry replaces this recent discovery of rearrangement elimination reaction (being called for short the TSRE reaction), the production technique of redesign diamond, polysilicon, chloroform and trichlorosilane, carbonic diester and chloro-formic ester, methyl alcohol and methane, compare with original production technique of these products, the preparation method of patent application of the present invention can solve from the source that produces the problem of discharge of wastewater, and the purpose that has reached significantly energy-saving and emission-reduction and reduced costs.

Background technology

I am engaged in the technical service work of enterprise for a long time, have successively applied for tens pieces of patents of invention.In the recent period, after quieting down, the applicant carefully sums up for technical service work and the innovation and creation thereof in past, discovery has a warp and woof to run through all the time wherein, summed up thus to replace to reset take the series connection of organic element chemistry and eliminated reaction (hereinafter to be referred as the TSRE reaction) for paper of topic, the theme of paper is definition and rule and the using value thereof of a kind of newfound universal synthetic method of discussion.The technical scheme of present patent application is a part of content in TSRE reaction paper, and this partial content is as described below:

Self-discovery Atherton-Todd reaction in decades, there is dispute in its reaction mechanism always, yet definition and rule with the TSRE reaction can reasonably be explained the Atherton-Todd mechanism, and can experiment arrangement (attached embodiment 1～11) be used for confirming the exactness that this " is reasonably explained ".

Fact proved, the Atherton-Todd reaction exists one to replace with same the connecting of TSRE reacting phase the course (formula 1) of eliminating reaction of resetting:

The phosphorous acid ester of four-coordination isomery under the chemical environment of alkalescence turns to the isomers 1 of three-fold coordination, and this is an intrinsic feature of phosphorons acid compound.And phosphorus (phosphine) the compound generation addition reaction that an intrinsic characteristic of tetracol phenixin is easy and three-fold coordination generates

Salt 2, according to the rule of TSRE reaction, 2 owing to containing a P-OH key and electron withdrawing group C1 atom, belongs to a kind of meta intermediate state, tandem rearrangement easily occurs after heating or illumination eliminate reaction, generates phosphoryl chloride 3 and chloroform, perhaps with H ₂When NR or HOR ' waited compound generation substitution reaction, series connection occurs to reset eliminated reaction, removes a HCl molecule, and collaborative target molecule 4 and the chloroform of generating.Its reaction mechanism meets the principle of pericyclic reaction, and it resets the stereospecificity that the product of eliminating generally has height, if product is crystal, the arrangement mode of this crystal should have systematicness and the directivity of height, should be generally the lattice of similar diamond-type.

So by the principle of above-mentioned TSRE reaction, the applicant has redesigned out the novel process of the preparation of diamond, polysilicon, chloroform, trichlorosilane, carbonic diester and these products of chloro-formic ester.

Basically can infer about the rule that the two keys of M=O are converted into the M-O singly-bound according to TSRE reaction: do not exist and orthocarbonic acid C (OH) that so far can not synthetic at occurring in nature ₄Under the chemical environment of excess NaOH and non-oxidation, can there be with the kenel of a or a ' (formula 11) in compound at normal temperatures:

A and a ' are very active intermediates, they and H ₂The activity that reduction occurs should compare CO ₂High several times are decades of times even, and we can be appropriate utilizes this point, is used for preparing methyl alcohol or methane (formula 12),

If pass into the CO of calculated amount in the reaction system of formula 12 ₂, so, at the Na that generates equivalent ₂CO ₃The time, can take off the aquatic formic acid of a part by 6; Can take off a part water by C and generate formaldehyde; D changes into methyl alcohol.The reaction of formula 6 can be carried out under the mild conditions of low temperature, low pressure, does not generally need to add traditional catalyzer, especially CO ₂Or the transformation efficiency of sodium carbonate can reach more than 90%, can say, this synthetic route is to prepare from now on the approach of optimal selection of the heavy industrialization of methyl alcohol or methane with carbonic acid gas.

Summary of the invention

The purpose of this invention is to provide a kind of method that this universal pattern of using the above-mentioned TSRE that is found in the recent period by the applicant to react prepares diamond, polysilicon, chloroform, trichlorosilane, carbonic diester and chloro-formic ester, methyl alcohol, methane product, compare with traditional and existing preparation method, have the effect of decrease cost and energy-saving and emission-reduction.

1, adamantine preparation

The synthetic route of old technique (formula 2)

In formula 2, C represents diamond

Novel process synthetic route (formula 3)

In formula 3, K and Zn represent germanium, silicon, lithium, potassium, sodium, H, zinc, magnesium, copper, iron, aluminium, indium, tin, samarium, silicon, manganese, antimony, preferred germanium, lithium, zinc, and K and Zn can be identical, can be not identical yet, R represents the alkyl or aryl with multiple functional group, also represents H, and C represents diamond.

The temperature of the whole process of formula 3 reactions is no more than 200 ℃, and the equipment of available normal pressure and routine carries out.Particularly product 8 belongs to the three-fold coordination phosphide, has with 5 or 5 ' identical function, also can be with the tetracol phenixin addition reaction through intermediate 9 and 10 preparation target compound C (formula 4):

By formula 4 as can be known, 8 do not have stoichiometric consumption in whole preparation process, can cyclic regeneration, and in fact 8 is the equal of the effect of a solvent borne catalyzer; And since 2010 Christian eras, tetracol phenixin was forbidden per unit area yield and sale by Chinese Government, the CCl of a large amount of by-products ₄Be put into " three wastes " product list, but still be allowed to prepare other products as the purposes of raw material.So, to compare with old technique, novel process energy-saving and emission-reduction, the effect that reduces costs are apparent.

The metal-salt 5 of combination phosphorous acid diester or tris phosphite 5 ' or triphenylphosphine and tetracol phenixin and metal K be that raw material prepares diamond, comprise several steps of following order:

The metal-salt 5 of the phosphorous acid diester of input calculated amount or tris phosphite 5 ' or triphenylphosphine and solvent, drop into the reactive metal powder K (preferred zinc or germanium or lithium) of calculated amount, start and stir, control 5 ℃～120 ℃ of temperature, stir after 2～4 hours, drip the tetracol phenixin of calculated amount, and the KOH solid that slowly adds calculated amount, insulation reaction 4～48 hours, then, through unit processes such as filtering, wash, be dry, get diamond.

2, the preparation of polysilicon

The synthetic route of old technique (formula 5)

In formula 5, Si represents polysilicon;

The synthetic route of novel process (formula 6)

In formula 6, Si represents polysilicon, and R represents the alkyl or aryl with multiple functional group, also represents H, and K and Zn represent zinc, magnesium, tin, copper, iron, aluminium, sodium, potassium, lithium, silicon, germanium, preferred zinc, copper, iron, and K and Zn can be identical, can be not identical yet,

The whole process of formula 6 reactions is no more than 200 ℃, and can use conventional equipment and carry out under normal pressure, particularly product 8 has with 5 or 5 ' identical function, also can be with the silicon tetrachloride reaction through intermediate 9 ' and 10 ' (formula 7), preparation target compound polysilicon Si

By formula 7 as can be known, 8 do not have stoichiometric consumption in whole preparation process, it is the equal of the effect of a solvent borne catalyzer, and how the silicon tetrachloride of 1 ton of polysilicon by-product of old explained hereafter more than 14 tons is developed the derived product of silicon tetrachloride or is processed unnecessary silicon tetrachloride, become China's polysilicon industry serious problem of the survival and development from now on that restricts, so, to compare with old technique, novel process energy-saving and emission-reduction, the effect that reduces costs are apparent.

The metal-salt 5 of combination phosphorous acid diester or tris phosphite 5 ' or triphenylphosphine and silicon tetrachloride and metal K be that raw material prepares polysilicon, comprise several steps of following order:

The metal-salt 5 of the phosphorous acid diester of input calculated amount or tris phosphite 5 ' or triphenylphosphine and solvent, drop into the reactive metal powder K (preferred zinc, copper, iron) of calculated amount, start and stir, control 5 ℃～120 ℃ of temperature, stir after 2～4 hours, drip the silicon tetrachloride of calculated amount, and the KOH solid that slowly adds calculated amount, insulation reaction 4～48 hours, then, through unit processes such as filtering, wash, be dry, get polysilicon.

3, the preparation of trichloromethane and trichlorosilane

From the above, the derived product of exploitation tetracol phenixin and silicon tetrachloride or process unnecessary tetracol phenixin or the silicon tetrachloride byproduct is the current urgent environmental protection task of arduousness again, China does not also have the Appropriate technology of the heavy industrialization of this respect at present, and the technological development of this respect still rests on the experimental phase.

Present patent application provides efficiently to be suitable for again heavy industrialization with CCl according to the principle of above-mentioned TSRE reaction ₄With SiCl ₄The synthesis route (formula 8) of preparation trichloromethane and trichlorosilane,

In formula 8, the expression meaning of R is identical with formula 3.

By formula 8 as can be known, phosphorous acid diester 14 can accomplish not have stoichiometric consumption in whole preparation process, it is the equal of the effect of a solvent borne catalyzer, perhaps can adopt the mode of coproduction phosphodiester 14 ' product, and, the equipment of the available conventional normal pressure of reaction of formula 8, the temperature of whole process is also below 150 ℃, conversion unit with 300～1000 ℃ of old techniques, 0.6～4MaP, and need add platinum and palladium precious metal again the method for the catalyzer of very easy inactivation compare, it is fairly obvious that novel process is carried out industrialized advantage.

Combination phosphorous acid diester 14 or tris phosphite 5 ' with tetracol phenixin or silicon tetrachloride be raw material, under alkaline condition, prepare trichloromethane or trichlorosilane, comprise several steps of following order:

The phosphorous acid diester 14 of input calculated amount or the tris phosphite 5 of calculated amount ' and highly basic resin or triethylamine and solvent, start and stir, control 5 ℃～120 ℃ of temperature, drip tetracol phenixin or the silicon tetrachloride of calculated amount, after insulation reaction 2～4 hours, drip the pure water of calculated amount, insulation reaction 2～24 hours gets trichloromethane A or trichlorosilane B by rectifying.

4, the preparation of carbonic diester and chloro-formic ester

The synthetic route (formula 9) for preparing carbonic diester or chloro-formic ester take tetracol phenixin as raw material.

In formula 9, K represents H, potassium, sodium, lithium, and R and R ' expression also represent H with the alkyl or aryl of multiple functional group, and R and R ' can be identical, also can be different.The 19th, the chloro-formic ester product series is the important source material of preparation carbonic diester product series and other fine chemicals, the 20th, and the carbonic diester series product.

60,000 tons, China's annual by-product tetracol phenixin waste material reaches few hundred thousand tonnes of and produce the carbonic diester series product per year, so the only reaction of formula 9 can be turned waste into wealth the tetracol phenixin of whole by-products, therefore the reaction of formula 9 has very large using value.

The synthetic route (formula 10) for preparing carbonic diester or chloro-formic ester take trichloromethane as raw material,

In formula 10, R represents the alkyl or aryl with multiple functional group, represents that also H, K represent H, potassium, sodium, lithium.

Combination tetracol phenixin or trichloromethane and ROH are that raw material prepares carbonic diester series product or chloro-formic ester series product, comprise several steps of following order:

Drop into ROK and the solvent of calculated amount, start and stir, control 40 ℃～135 ℃ of temperature, drip tetracol phenixin or the trichloromethane of calculated amount, then insulation reaction 2～4 hours adds KOH or the water of calculated amount, perhaps passes into oxygen and carries out oxidation, insulation reaction is 4～8 hours again, gets chloro-formic ester by rectifying; By crystallization, filtration, the dry carbonic diester that gets.

Employing formula 9 prepares carbonic diester or chloro-formic ester with the reaction of formula 10, non-wastewater discharge, and reduce costs more than 10% than existing production technique.

5, the preparation of methyl alcohol and methane

As everyone knows, prepare the realization of the heavy industrialization of methyl alcohol take carbonic acid gas as raw material, have huge meaning for the realization of the target of carbon emission reduction amount from now on, but traditional technological core is the shortening synthetic method.In decades, it screens catalyzer, CO so far in any case ₂Transformation efficiency still can not surpass 20%, make the production of enterprise can not produce a bit economic benefit.And due to the difference of essence being arranged according to the reaction mechanism of the novel process of above-mentioned TSRE reaction designing and traditional Catalytic processes, generally do not consider to add the CO of other catalyzer, particularly novel process ₂Transformation efficiency become several times to increase, therefore the raising of its economic benefit is fairly obvious.

Novel process synthetic route (formula 13):

In formula 13, Na represents NH ₃, sodium, potassium, lithium, calcium, zinc, copper, iron, aluminium;

Combination phosgene or sodium carbonate and sodium hydroxide are that raw material prepares sodium methylate or methyl alcohol or methane product, comprise several steps of following order:

Drop into 30～50% NaOH of calculated amount, start and stir, control one of 5 ℃～100 ℃ of temperature and pressure below normal atmosphere, slowly pass into or drop into the CO of calculated amount ₂Or NaCO ₃, then insulation reaction 2～24 hours slowly passes into or drops into hydrogen or the sodium borohydride of calculated amount, continues insulation reaction 2～24 hours, then the water in the clean reaction system of evaporate to dryness, reclaims simultaneously the methane gas of by-product; The anhydrous methanol that adds calculated amount, the sodium methylate that dissolving generates, according to the method for routine, preparation becomes 18% sodium methylate commodity, perhaps before adding anhydrous methanol, directly passes into the CO of calculated amount ₂, methanol and Na ₂CO ₃

Specific embodiments

Embodiment 1

Select high-purity diphenyl phosphite (0.2mol) and high pure benzene solvent (200g) or tetrahydrofuran (THF) (100g), drop in reaction flask, start and stir, under the condition of isolated air and water, drop into high purity lithium powder (0.2mol) or high-purity LiOH (0.2mol), slowly heat up, control 40～120 ℃ of temperature, reflux, stirring reaction 8～40 hours, the benzene liquid 5 of diphenyl phosphite lithium, content 15% left and right, yield 95%.

Embodiment 2

Under the condition of strict isolated air and water, drop into 5 (0.2mol) of embodiment 1 preparation and highly pure active magnesium powder or lithium powder (0.2～1.2mol) and tetrahydrofuran (THF) or toluene (300g), the startup stirring, control 10～120 ℃ of temperature, stir after 2～4 hours, drip high-purity tetracol phenixin (0.2mol), after dripping off, insulation reaction 4～48 hours is down to normal temperature, standing, filter washing, oven dry, get diamond 1.1～1.6g, yield 40～60%.

Embodiment 3

under the condition of strict isolated air and water, drop into 99% triphenyl phosphite 5 ' (0.2mol) or triphenylphosphine (0.2mol) and high pure tetrahydrofuran (100g) or toluene (300g), drop into again high-purity active zinc powder or germanium powder (0.2～1.2mol), start and stir, be warming up to backflow, stirred 2～4 hours, then controlling 5 ℃ of temperature extremely refluxes, drip high-purity tetracol phenixin (0.2mol), after dripping off, insulation reaction 4 hours, slowly add again high-purity KOH (0.2mol) solid, after adding, continued insulation reaction 4-48 hour, be down to normal temperature, standing, filter, washing, oven dry, get diamond 1.6～2.0g, yield 60～80%.

Embodiment 4

Under the condition of strict isolated air and water, the trimethyl phosphite (0.2mol) of input 99% and high pure tetrahydrofuran or dimethylbenzene (100g～200g), start and stir, control 5 ℃ of temperature and extremely reflux, drip high-purity tetracol phenixin, after dripping off, insulation reaction 2～4 hours, then, control 0～5 ℃ of temperature, slowly add high-purity N aOH solid (0.2mol) and highly pure active copper powder (0.2～1.2mol) mixture, after adding, continue insulation reaction 4～48 hours, and be down to normal temperature, standing, filter, washing, oven dry gets diamond 1.9g.

Embodiment 5

Under the condition of strict isolated air and water, drop into 99% dimethylphosphite (0.2mol) and tetrahydrofuran (THF) (120g), start and stir, controlling 5 ℃ of temperature extremely refluxes, slowly add Na or each 0.2mol of NaOH of 99%, insulation reaction dropped into active zinc powder (0.2～1.2mol) after 4 hours, continue again to stir 2～4 hours, drip 99% silicon tetrachloride (0.2mol), after dripping off, continued insulation reaction 4～48 hours, cooling, standing, filter washing, oven dry gets polysilicon 4.8g.

Embodiment 6

Drop into 99% trimethyl phosphite (0.2mol) and dimethylbenzene (200g) or tetrahydrofuran (THF) (100g), drop into again high-purity active zinc powder (0.2～1.2mol), start and stir, controlling 5 ℃ of temperature extremely refluxes, stir after 2～4 hours, drip high purity silicon tetrachloride (0.2mol), after dripping off, continued insulation reaction 4～8 hours, then slowly add 99% NaOH (0.2mol), after adding, continued insulation reaction 4～48 hours, cooling, standing, filter washing, oven dry gets polysilicon 5.3g.

Embodiment 7

Drop into 98% dimethylphosphite or trimethyl phosphite 5 ' (0.2mol) and tetrahydrofuran (THF) (100g), and highly basic resin (0.2mol), start and stir, control 5 ℃～120 ℃ of temperature, and the tetracol phenixin of dropping 98% or silicon tetrachloride (0.2mol～1mol), after dripping off, insulation reaction 2～24 hours, method by rectifying steams trichloromethane or trichlorosilane, content 98%, yield 90%.

Embodiment 8

Drop into 98% trimethyl phosphite (0.2mol) and toluene (300g) or tetrahydrofuran (THF) (100g), start and stir, control 5 ℃～120 ℃ of temperature, drip 98% silicon tetrachloride (0.2mol) or tetracol phenixin (0.2mol), after dripping off, insulation reaction 2～4 hours, then slowly add pure water (0.2～0.4mol), insulation reaction 4～24 hours, the method by rectifying steams trichloromethane or trichlorosilane, content 98%, yield 90%.

Embodiment 9

Drop into sodium phenylate (0.2mol～0.4mol) and toluene (100g), start and stir, control 40 ℃ of temperature～backflow, drip tetracol phenixin (0.2mol), insulation reaction 2～8 hours, then slowly add 98% NaOH or water (0.2mol), after adding, insulation reaction 4～8 hours is by the method for rectifying, steam the phenyl chloroformate in reaction system, content 98%, then cooling, standing, crystallization, filter, drying gets the dipheryl carbonate crystalline esters, content 99%, transformation efficiency 95%.

Embodiment 10

Drop into sodium phenylate (0.2mol or 0.4mol) and toluene (100g), start and stir, control 40 ℃ of temperature～backflow, drip trichloromethane (0.2mol), then insulation reaction 4～8 hours passes into oxygen or air under illumination, insulation reaction 4～8 hours, stop logical oxygen, by the method for rectifying, steam the phenyl chloroformate in reaction system, content 98%, then cooling, standing, drying is filtered in crystallization, get the dipheryl carbonate crystalline esters, content 97%, transformation efficiency 95%.

Embodiment 11

Drop into triphenylphosphine (0.2mol) and highly pure active germanium powder or silica flour (0.2～1.2mol) and tetrahydrofuran (THF) or tetracol phenixin (100g), start and stir, control 5 ℃ of temperature～backflow, stirred 2～4 hours, begin to drip tetracol phenixin (0.2mol), stirring reaction 4～8 hours slowly adds again 99% KOH (0.2mol), insulation reaction 4～48 hours, cooling, standing, filter, drying gets diamond 1.8～2.2g.

Embodiment 12

Under the condition of the air in reactor being drained with vacuum, (0.8～1.6mol) aqueous solution starts and stirs, and controls one of 5 ℃～100 ℃ of temperature and pressure below normal atmosphere, slowly passes into CO to drop into 30～50% NaOH ₂Gas (0.2mol) or input Na ₂CO ₃(0.2mol), insulation reaction 2～24 hours, then, slowly pass into hydrogen (0.8～1mol) or drop into sodium borohydride (0.2～0.8mol), insulation reaction is 2～24 hours again, step-down, cooling, beginning water in the evaporate to dryness reaction system under normal pressure, simultaneously constantly there is methane gas to overflow, reclaims the purposes as commodity.Then (60～100g), 40 ℃ were stirred 2 hours, standing, filtered, and the mother liquor that filters is become 18% sodium methylate liquid product by the way preparation that routine concentrates to add anhydrous methanol.

Embodiment 13

Process before adding anhydrous methanol is identical with embodiment 12.

During reaction end add anhydrous methanol in above-described embodiment 12 before, pass into CO ₂Gas (0.2～0.8mol), control 5～40 ℃ of temperature, then insulation reaction 2～12 hours, steams the methyl alcohol of generation under normal pressure, content 98%, yield 60～80%.

Embodiment 14

Drop into 30～50% sodium hydroxide (0.8～1mol), start and stir, control 5～100 ℃ of temperature, slowly pass into carbonic acid gas (0.2mol) or drop into sodium carbonate (0.2mol), insulation reaction 2～24 hours, evaporate to dryness water purification under vacuum, cooling, standing, get the mixture solid of a and a ', the transformation efficiency 95% of carbonic acid gas or sodium carbonate.

The preparation of embodiment 15 orthoformic acid trisodium b

The sodium formiate (0.2mol) of input 98% and 30% NaOH (0.2～0.4mol), start and stir, control 5～100 ℃ of temperature, insulation reaction 2～24 hours, evaporate to dryness water purification under vacuum, cooling, standing, get compound b, the transformation efficiency 95% of sodium formiate.

The preparation of embodiment 16 methylene glycol sodium c

The paraformaldehyde (0.2mol) of input 94% or the NaOH (0.2～0.4mol) of 36% formalin 17g and 30%, start and stir, control 5～100 ℃ of temperature, insulation reaction 2～24 hours, evaporate to dryness water purification under vacuum, cooling, standing, get compound c, the transformation efficiency 95% of formaldehyde.

The preparation of embodiment 17 formic acid and formaldehyde

(50～100g), startup is stirred, and passes into CO to drop into b or c compound each (0.2mol) and water ₂(0.2～0.4mol) or acid (0.2～0.4mol), the temperature remains within the normal range stirred 1～2 hour, got the aqueous solution of formic acid or formaldehyde, the transformation efficiency 95% of b or c.

Claims

The metal-salt 5 of combination phosphorous acid diester or tris phosphite 5 ' or triphenylphosphine and tetracol phenixin and metal K be that raw material prepares diamond product, its technical characterictic is synthetic route as described below:

In formula A, C represents diamond product; K and Zn represent germanium, silicon, lithium, potassium, sodium, H, zinc, magnesium, copper, iron, aluminium, indium, tin, samarium, silicon, manganese, antimony; Preferred zinc, germanium, lithium, K and Zn can be identical, can be not identical yet, R represents the alkyl or aryl with multiple functional group, also represents H.
2. make up the metal-salt 5 of inferior phosphide diester or tris phosphite 5 ' or triphenylphosphine and silicon tetrachloride and metal K be that raw material prepares polysilicon product, its technical characterictic is synthetic route as described below:

In formula B, Si represents polysilicon product; K and Zn represent zinc, magnesium, tin, copper, iron, aluminium, sodium, potassium, lithium, silicon, germanium, preferred zinc, copper, iron, and K and Zn can be identical, can be not identical yet, R represents the alkyl or aryl with multiple functional group, also represents H.
Combination phosphorous acid diester 14 or tris phosphite 5 ' with tetracol phenixin or silicon tetrachloride be raw material, under the base catalysis condition, prepare trichloromethane or trichlorosilane, its technical characterictic is synthetic route as described below:

In formula C, R represents the alkyl or aryl with multiple functional group.
4. combination tetracol phenixin or trichloromethane and ROK are that raw material prepares carbonic diester series product or chloro-formic ester series product, and its technical characterictic is synthetic route as described below:

In formula D, K represents H, potassium, sodium, lithium, and R and R ' expression also represent H with the alkyl or aryl of multiple functional group, and R and R ' can be identical, also can be different.
5. combined carbon dioxide or sodium carbonate and NaOH are that raw material prepares methyl alcohol or sodium methylate or methane product, and its technical characterictic is synthetic route as described below:

In formula E, Na represents sodium, potassium, lithium, NH ₃, calcium, zinc, copper, iron, aluminium.
6.a, a ', b, c be the compound with following structural:
7. according to claim 6, utilize a, a ', b, c compound to prepare methyl alcohol or methane or its mixture, perhaps utilize b to prepare formic acid; Perhaps utilize c to prepare formaldehyde.