CN101544539A - Method for producing polymer grade ethylene glycol and co-producing methyl glycolate - Google Patents
Method for producing polymer grade ethylene glycol and co-producing methyl glycolate Download PDFInfo
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- CN101544539A CN101544539A CN200910061855A CN200910061855A CN101544539A CN 101544539 A CN101544539 A CN 101544539A CN 200910061855 A CN200910061855 A CN 200910061855A CN 200910061855 A CN200910061855 A CN 200910061855A CN 101544539 A CN101544539 A CN 101544539A
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Abstract
The invention discloses a method for producing polymer grade ethylene glycol and co-producing methyl glycolate, which comprises the following steps that: feed gas produced by taking coal, natural gas or residual oil as a raw material is subjected to purification treatment to obtain carbon monoxide and hydrogen through pressure varying absorption; the carbon monoxide, the hydrogen and auxiliary raw materials, namely industrial methanol, oxygen and nitrogen oxide are subjected to processes such as nitrosation reaction, carbonylation reaction, hydrogenation reaction, rectification separation, tail gas purification treatment and the like to obtain the ethylene glycol and the methyl glycolate; and the yield proportion of the ethylene glycol and the glycollic acid can be adjusted by controlling the hydrogenation reaction and the rectification process. In the method, the carbonylation reaction is performed on a Pd/alpha-Al2O3 catalyst added with two additives, and the carbonylation reaction is performed on a Cu-SiO2 or Cu-Cr2O3 or Cu-Zn-Al methanol catalyst, wherein the conversion ratio of the CO and the H2 is over 99.9 percent; and the selectivity is over 98 percent. Compared with the prior method for producing the ethylene glycol and the methyl glycolate, the method has the characteristics of low cost and high benefit.
Description
Technical field
The present invention relates to a kind of extensive be that raw material is produced CO and H with coal, Sweet natural gas or residual oil
2Synthetic gas is produced the method for ethylene glycol (EG) and methyl glycolate (MG).
Background technology
Ethylene glycol is a kind of important chemical industry raw material, is widely used in synthesizing polyester, tensio-active agent, frostproofer and explosive etc., and the world will consume 2,000 ten thousand tons of ethylene glycol every year, is the alcohols material of second largest synthetic after methyl alcohol.Methyl glycolate is a kind of important fine chemical product, is used to produce oxyacetic acid etc.The production method of ethylene glycol mainly adopts ethylene oxy to change into oxyethane at present, and oxyethane hydrolysis again obtains aqueous glycol solution, obtains ethylene glycol through rectifying again, and this method exists the raw materials consumption amount big, energy consumption height, the shortcoming that production cost is high.
Last century the eighties, U.S.'s union carbide corporation and company of Ube Industries Ltd. have developed jointly by CO coupling system dibutyl oxalate, the method for repeated hydrogenation preparing ethylene glycol.The principle of this method is as follows:
The first step oxonation: CO+C
4H
9ONO → (C
4H
9OCO)
2+ NO
The second step hydrogenation reaction: (C
4H
9OCO)
2+ H
2→ C
4H
9OH+CH
2OHCH
2OH
The 3rd step nitrosation reaction: C
4H
9OH+NO+1/2O
2→ C
4H
9ONO+H
2O
This method is with CO and H
2Be raw material, by step synthesizing glycols such as carbonylation, hydrogenation, have the reaction conditions gentleness, raw materials consumption is low, the characteristics that production cost is low, but do not see the industrialization report that this method is follow-up.
Domestic also have how tame research unit carrying out the work of this respect, as (the CN1054765A of Fujian Inst. of Matter Structure, Chinese Academy of Sciences, 1991), (CN1149047 of University Of Tianjin, 1997) and Shanghai coking (CN101190884A, 2008), the work of domestic these units mainly concentrates in dimethyl oxalate (DMO) or the research and development of oxalic acid diethyl ester (DEO) synthetic, yet there are no the patent report with dimethyl oxalate synthesized polymer level ethylene glycol.
Polymerization-grade ethylene glycol is mainly used to synthesizing polyester, because the impurity of trace can produce great effect to the quality of polyester, the aldehyde as 10/1000000ths, ketone compounds will cause the polymerization degree of polyester to reduce, and make product defective.Thereby polymerization-grade ethylene glycol has strict demand to foreign matter content, and its index is equivalent to the standard of premium grads in the ethylene glycol GB, and the standard of China's ethylene glycol sees Table 1.
As seen from Table 1, the premium grads of ethylene glycol and the difference of acceptable end product mainly are the difference of aldehyde and ultraviolet transmittance, and acceptable end product is to these two no standards.The ultraviolet transmittance is the index of two key foreign matter contents in the metering ethylene glycol, and it is similar to the influence of synthesizing polyester and aldehyde, ketone, so strict demand is arranged.
The foreign matter content of the ethylene glycol that present employing dimethyl oxalate method of hydrotreating makes is many more than the oxyethane hydrolysis method, impurity is nearly tens kinds in the ethylene glycol that obtains with the dimethyl oxalate method of hydrotreating, as ethanol, methylcarbonate, 1-butanols, 2-butanols, butyleneglycol, aldehyde, ketone and ester etc., the feasible ethylene glycol purifies and separates difficulty that makes with the dimethyl oxalate hydrogenation method.
The deficiency of existing method mainly contains the following aspects:
1, mostly be the relevant patent of synthesizing dimethyl oxalate in the present disclosed method, fail preparing ethylene glycol by using dimethyl oxalate plus hydrogen is combined consideration, disclosed dimethyl oxalate hydrogenation patent mostly is the catalyzer patent simultaneously.
2, partial monopoly is than the technologies such as raw material gas purifying, methyl nitrite circulate, dimethyl oxalate synthesizes that disclose of system, and its raw material gas purifying adopts the ZnO sweetening agent, and index is outlet total sulfur＜1.5 * 10
-6(v/v), this relative noble metal catalyst requires total sulfur＜0.1 * 10
-6(v/v), its sulphur content severe overweight will inevitably make poisoning of catalyst and shortens the life-span; H in the high-content CO gas
2Adopt the catalyst of load platinum metals to remove, but fail to mention selectivity of catalyst, not mentioned CO and O
2The CO significant loss that causes of side reaction.
3, the method for in addition patent disclosure has been arranged synthesizing dimethyl oxalate and by-product methylcarbonate, the selectivity of synthetic catalyst fails to reach more than 99%, has increased product separation purification difficulty.
4, produce the technological line of ethylene glycol through dimethyl oxalate, the height of its actual application value depends on that can product ethylene glycol reach polymerization-grade, and is all not mentioned in disclosed method and the document at present.
Summary of the invention
The object of the present invention is to provide the method for a kind of reaction conditions gentleness, production polymer grade ethylene glycol and co-producing methyl glycolate that cost is low, and be suitable for large-scale production.
A kind of method of producing polymer grade ethylene glycol and co-producing methyl glycolate of the present invention mainly contains following five steps reaction:
Carbongl group synthesis reaction: 2CO+2CH
3ONO → (CH
3OCO)
2+ 2NO
Nitrosation reaction: 2CH
3OH+2NO+1/2O
2→ 2CH
3ONO+H
2O
Hydrogenation reaction 1:(CH
3OCO)
2+ 2H
2→ CH
3OCOCH
2OH+CH
3OH
Hydrogenation reaction 2:(CH
3OCO)
2+ 2H
2→ CH
2OHCH
2OH+CH
3OH
Hydrogenation reaction 3:CH
3OCOCH
2OH+4H
2→ CH
2OHCH
2OH+CH
3OH
Technical scheme of the present invention is as follows:
A kind of method of producing polymer grade ethylene glycol and co-producing methyl glycolate is that the unstripped gas that raw material makes adsorbs and smart desulfurization through dedusting, wet desulphurization, decarburization, PSA transformation with coal, Sweet natural gas or residual oil, isolates CO and H
2, isolated CO is under the participation of methyl nitrite, by the Pd/ α-Al of two kinds of auxiliary agents of a kind of interpolation
2O
3The catalyzer oxo process is produced dimethyl oxalate, and product obtains highly purified dimethyl oxalate through separation, and tail gas is through the nitrosification recycling utilization; The dimethyl oxalate that this process obtains is at a kind of Cu-SiO
2Or Cu-Cr
2O
3Or the catalysis of Cu-Zn-Al catalyst for methanol is following and H
2Reaction obtains ethylene glycol and methyl glycolate, and product obtains ethylene glycol and methyl glycolate through extraction, rectifying separation, regulates the fractional yield that working condition changes ethylene glycol and methyl glycolate, to be fit to the market requirement.
In the method for the present invention, described unstripped gas is isolated CO and H through dedusting, wet desulphurization, decarburization, the absorption of PSA transformation and smart desulfurization
2, make total sulfur＜0.1ppm among the CO, CO purity 〉=98.5%; H
2Middle total sulfur＜0.1ppm, H
2Purity 〉=99%.
Contain 0.1%-1.5%H in the CO gas that described PSA transformation fractionation by adsorption goes out
2Adopt the oxygenation catalytic eliminating, dehydrogenation catalyst be a kind of be carrier with the aluminum oxide, palladium and/or platinum are active ingredient, and 2-4 kind MOx is an auxiliary agent, and M is sodium, potassium, magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten or cerium, the composition of catalyzer is counted with the carrier quality: palladium 0.01%～2% and platinum 0.01%～1%, perhaps palladium 0.01%～2% or platinum 0.01%～1%, the total amount of 2-4 kind MOx is 1%～20%, H in the CO gas after the catalytic dehydrogenation
2＜100 * 10
-6, O
2＜1000 * 10
-6, the loss amount of CO＜0.3%.
After the CO that described PSA transformation fractionation by adsorption goes out removes hydrogen, carry out carbongl group synthesis reaction, at the Pd/ α-Al of two kinds of auxiliary agents of a kind of interpolation with methyl nitrite
2O
3Synthesizing dimethyl oxalate on the catalyzer, this catalyzer is carrier with the Alpha-alumina, palladium is an active ingredient, 2 kinds of MOx are auxiliary agent, M is magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, copper, zinc, molybdenum or tungsten, the composition of catalyzer is counted with the carrier quality: palladium 0.01%～0.75%, the total amount of 2 kinds of MOx are 0.1%～20%, the selectivity of dimethyl oxalate synthetic catalyst〉99%.
In the method for the present invention, the gas cooling that carbongl group synthesis reaction comes out is isolated most dimethyl oxalate product to 70-80 ℃, and this product further cooling obtains highly purified dimethyl oxalate product, purity〉99.5%.
In the method for the present invention, described methyl nitrite adopts NO, methyl alcohol and purity〉90% industrial oxygen reaction makes, and presses NO/O
2=4～8 mol ratio is mended into industrial oxygen, presses CH
3The mol ratio of OH/NO=1～3 adds methyl alcohol, and controlled temperature makes above-mentioned being reflected under the gas phase condition carry out product C H
3ONO adopts the pressurization condensation separation.
CH takes place through the nitrosification reprocessing cycle in the tail gas after the dimethyl oxalate that carbongl group synthesis reaction produces is separated
3ONO, the CO recycle, tail gas and industrial oxygen that part contains NO enter tail gas absorber at the bottom of tower, use the sodium carbonate solution of mass concentration 5%-20% to add absorption of N O from cat head, the torch burning emptying of reducing internal heat of other gases, the Sodium Nitrite that from absorption liquid, obtains or the NO recycle takes place.
In the method for the present invention, the product that oxo process is produced, the high-purity oxalic acid dimethyl ester that obtains through condensation separation is with H
2Press H
2/ dimethyl oxalate=10～100 mol ratios enter hydrogenator, a kind of Cu-SiO of filling in the hydrogenator
2Or Cu-Cr
2O
3Or Cu-Zn-Al catalyst for methanol (catalyzer is from US 5345005 or US 4677234 or US 4628128 or clear 57-123127 of JP or commercial methanol catalyzer).The hydrogenator inlet temperature is 100～250 ℃, and pressure 0.5～4MPa hydrogenation products is mainly ethylene glycol and methyl glycolate, and ethanol, butyleneglycol, methylcarbonate, aldehydes and ketone by product are perhaps arranged simultaneously.
The method of production polymer grade ethylene glycol and co-producing methyl glycolate of the present invention is regulated the H of hydrogenation reaction
2/ dimethyl oxalate mol ratio, temperature and air speed condition can change the ratio of glycol product and methyl glycolate.
The concrete steps of method that the present invention produces polymer grade ethylene glycol and co-producing methyl glycolate are as follows:
1, the preparation of unstripped gas
With coal, Sweet natural gas or residual oil is that raw material is made unstripped gas, and the gas that makes is through dedusting, wet desulphurization, decarburization, the absorption of PSA transformation and smart desulfurization, separation of C O and H
2, purity 〉=98.5% of CO after separating, H
2Purity 〉=99%, CO removes oxo process, H
2Burring dimethyl phthalate hydrogenation.
2, dimethyl oxalate is synthetic
CO that a, transformation fractionation by adsorption go out earlier in dehydrogenation reactor by O
2/ H
2=0.6 ~ 0.9 mole matches well oxygen and removes H
2Dehydrogenation reactor is a shell-and-tube reactor, adopt the water management temperature of reaction between pipe, dehydrogenation catalyst be above-mentioned a kind of be carrier with the aluminum oxide, palladium and/or platinum are active ingredient, 2-4 kind MOx is an auxiliary agent, and M is the catalyzer of sodium, potassium, magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten or cerium, H in the CO gas after the catalytic dehydrogenation
2＜100 * 10
-6, O
2＜1000 * 10
-6, the loss amount of CO＜0.3%.Reactor inlet temperatures is 100～300 ℃, H in the reactor outlet gas
2≤ 100 * 10
-6, O
2≤ 1000 * 10
-6, the CH that this exit gas comes with the methyl nitrite storage tank
3ONO is mixed into the molecular sieve dehydration tower, and water-content is less than≤100 * 10 in the dehydrated raw material gas
-6, dehydrated raw material gas enters carbonyl synthesis reactor;
B, the inlet temperature of carbonyl synthesis reactor is 90～160 ℃, pressure 0.1～0.4MPa, a kind of dimethyl oxalate synthetic catalyst of interior filling, this catalyzer be above-mentioned be carrier with the Alpha-alumina, palladium is an active ingredient, 2 kinds of MOx are auxiliary agent, M is a magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, copper, zinc, the catalyzer of molybdenum or tungsten, reacted gas cooling to 70～80 ℃, isolate most of dimethyl oxalate, obtain high-purity oxalic acid dimethyl ester solid through further cooling off, residual gas absorbs the uncooled dimethyl oxalate that gets off through the dimethyl oxalate absorption tower, obtain the dimethyl oxalate methanol solution, after this purified solution as the dimethyl oxalate hydrogenating materials;
C, the gas that comes out from the dimethyl oxalate absorption tower enter the methyl nitrite regenerator column, press NO/O in the methyl nitrite regenerator column
2=4～8 mol ratio is mended the industrial oxygen into oxygen level 〉=90%, methyl alcohol adds from cat head by the mol ratio of methyl alcohol/NO=1～3, the gas delivery part first alcohol and water that goes out from cat head, condensation separation methyl nitrite and coagulate gas then, isolated methyl nitrite enters the methyl nitrite storage tank, with gas circulation is to carbonyl synthesis reactor with fixed attention, all the other coagulate gas and enter exhaust gas processing device methyl nitrite through evaporation in the storage tank; Methyl alcohol and water cycle that tower bottom flow goes out are removed methanol rectifying tower, and smart distilled methanol loop is used;
D, exhaust gas processing device are mainly used in the processing of NO in the tail gas, and tail gas and industrial oxygen are pressed NO/O
2=4～8 mol ratios enter at the bottom of tower, and the NO absorption liquid adds from cat head, and the NO absorption liquid is the sodium carbonate solution of mass concentration 5～20%; Gas torch burning emptying after the processing;
3, hydrogenation preparing ethylene glycol and methyl glycolate
The H that dimethyl oxalate that a, condensation go out and the barkite alcoholic solution that comes out from the dimethyl oxalate absorption tower go out with PSA transformation fractionation by adsorption
2Press H
2/ dimethyl oxalate=10～100 mol ratios enter hydrogenator, and hydrogenator is a shell and tube reactor, adopt hot water shifting heat between pipe, and the material inlet temperature is 100～250 ℃, and pressure 0.5～4.0MPa adopts a kind of Cu-SiO in hydrogenator
2Or Cu-Cr
2O
3Or Cu-Zn-Al catalyst for methanol (catalyzer is from US5345005 or US4677234 or US4628128 or clear 57-123127 of JP or commercial methanol catalyzer).Hydrogenation products flows out from reactor bottom, H
2Recycle, product liquid enter hypomere in the pre-separation tower;
The tower top temperature of b, pre-separation tower is between 63～75 ℃, and tower still temperature is at 140～170 ℃, and overhead product is the ethanol of methyl alcohol and trace etc., can be directly as nitrosifying methanol feedstock; Extract liquid from the tower middle part, this liquid is the mixture of methyl glycolate and dimethyl oxalate; Bottom product is an ethylene glycol etc.;
C, the product liquid that pre-separation tower middle part is extracted enter the middle and lower part of dibasic acid esters knockout tower, the dibasic acid esters knockout tower is a rectifying tower, and tower top temperature is between 141～152 ℃, and overhead product is a methyl glycolate, tower still temperature is between 155～165 ℃, and bottom product is a dimethyl oxalate etc.;
D, pre-separation Tata still glycol product obtain the ethylene glycol of polymerization-grade through extraction, rectifying;
The H of e, adjusting hydrogenation reaction
2The liquid air speed of/dimethyl oxalate molar ratio, dimethyl oxalate obtains the hydrogenation products of different ratios; The tower kettle product of pre-separation tower directly can be delivered to the ethylene glycol knockout tower when not needing methyl glycolate, control tower still and tower top temperature make dimethyl oxalate and methyl glycolate distillate from cat head, and then enter hydrogenator.
Advantage of the present invention:
1, the present invention is to be a kind of C of using of background with the suitability for industrialized production
1The method of chemical production polymerization-grade ethylene glycol and methyl glycolate is a raw material with coal, Sweet natural gas or the residual oil of cheapness, and the petroleum path of present relatively oxidation of ethylene hydrolysis has good in economic efficiency, characteristic of low energy consumption.
2, the objective of the invention is to produce polymer grade ethylene glycol and co-producing methyl glycolate.
3, gas sweetening isolation technique such as smart desulfurization, transformation absorption are adopted in the wood invention, can make total sulfur in the unstripped gas＜0.1 * 10
-6, thereby can prolong selective dehydrogenation catalyzer, dimethyl oxalate synthetic catalyst and hydrogenation catalyst work-ing life.
4, the selective dehydrogenation catalyzer that uses in the high concentration CO source of the gas of the present invention adopts noble metal catalyst, this catalyst selectivity height, CO loss amount＜0.3%; The space-time yield of dimethyl oxalate synthetic catalyst can reach 750g/Lh, selectivity〉99.5%; Hydrogenation catalyst adopts ripe catalyzer active and that selectivity is all excellent, wherein DMO transformation efficiency〉99%, the overall selectivity of EG and MG〉98%, effectively avoid some separation difficulty and influenced the by product generation of product quality.
5, the present invention is a raw material with coal, Sweet natural gas or residual oil, and prepared unstripped gas is isolated CO and H by pressure swing adsorption
2, wherein CO is used for dimethyl oxalate and synthesizes H
2Be used for hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, fully reasonable use unstripped gas.And employing PSA pressure swing adsorption separation of C O and H
2Possess skills maturation, characteristics that production cost is low are fit to large-scale CO and H
2Industrial preparation.
6, the market of dimethyl oxalate is limited at present, and the ethylene glycol market capacity is very big, the present invention combines synthetic synthesizing with ethylene glycol of dimethyl oxalate, greatly expanded the industrial scale of oxo process, but because dimethyl oxalate reactor byproduct steam and superheated water, but and the steam of 180～200 ℃ of dimethyl oxalate hydrogenation workshop section by-products, the ethylene glycol centrifugal station needs 100～200 ℃ steam, therefore the steam of each workshop section's by-product is rationally utilized, make full use of reaction heat, avoided the waste of the energy, saved production cost.
7, the mode of this process using condensation is separated whole methyl nitrites, and reduction vaporization makes whole dimethyl oxalate synthetic coupling process simplified control through being metered into carbonyl synthesis reactor, and the intractability of tail gas is reduced.
8, vent gas treatment adopts sodium carbonate solution to join the unreacted NO of oxygen absorption, makes it to be converted into Sodium Nitrite and can be used as commodity selling, the gas torch burning emptying after alkali lye absorbs.
9, the methyl alcohol in ethylene glycol production can be got back to the dimethyl oxalate synthesizing section, thereby realizes the circulation of methyl alcohol, and whole flow process is removed CO, O
2And H
2And outside the NO of small amount of supplemental, do not need extra raw material.
10, the ethylene glycol that obtains of hydrogenation can obtain the ethylene glycol of polymerization-grade through methods such as rectifying, extractions.
11, by regulating processing parameter etc., can change the output of ethylene glycol and methyl glycolate, to adapt to the demand in market.
Description of drawings
Fig. 1 is a process flow diagram of producing polymer grade ethylene glycol and co-producing methyl glycolate.
Among the figure, 1-gas making, 2-dedusting, the 3-wet desulphurization, the smart desulfurization of 4-, the absorption of 5-PSA transformation, the 6-dehydrogenation reactor, 7-molecular sieve dehydration tower, 8-carbonyl synthesis reactor, 9-dimethyl oxalate absorption tower, 10-methyl nitrite regenerator column, 11-methyl nitrite storage tank, the 12-tail gas absorber, 13-dimethyl oxalate dissolving tank, 14-methanol rectifying tower, the thick methyl alcohol storage tank of 15-, 16-dimethyl oxalate hydrogenator, 17-pre-separation tower, 18-refined methanol storage tank, 19-dibasic acid esters knockout tower, 20-methyl glycolate storage tank, 21-ethylene glycol extraction tower, 22-ethylene glycol rectifying tower, 23-finished product ethylene glycol storage tank, 24-extraction agent storage tank, I, III, the IX preheater, V, the VI condenser, II, IV, VII, VIII, X, XI, XII, XIII, the XIV interchanger.
Embodiment
Idiographic flow of the invention process as shown in Figure 1, this flow process can be divided into 6 parts such as the separation, vent gas treatment of regeneration, dimethyl oxalate hydrogenation, the hydrogenation products of preparation, oxo process dimethyl oxalate, the methyl nitrite of gas raw material.The invention will be further described below in conjunction with accompanying drawing:
1, the preparation of gas raw material: be that raw material is made unstripped gas at first with coal, Sweet natural gas or residual oil, the synthetic gas that comes out from vapourizing furnace 1 removes organosulfur and inorganic sulfur remaining the source of the gas through dedusting 2, wet desulphurization 3, smart desulfurization 4, makes total sulfur volume content＜0.1 * 10
-6, gas obtains CO 〉=98.5% and H by PSA transformation absorption 5 separation after the desulfurization
2〉=99% gas is pressed O in CO
2/ H
2=0.6～0.9 volume ratio is allocated oxygen into, and the CO behind the oxygenation is heated to 100～250 ℃ through preheater I, enters dehydrogenation reactor 6 and removes H among the CO
2, H among the CO after the dehydrogenation
2Volume content＜100 * 10
-6, O
2＜1000 * 10
-6, CO loss amount＜0.3% during dehydrogenation.
2, oxo process dimethyl oxalate: gas after the dehydrogenation and the CH that comes to methyl nitrite storage tank 11
3The uncondensed gas that ONO and condenser VI come out is mixed through 7 dehydrations of molecular sieve dehydration tower, dehydration back gas volume of water content＜100 * 10
-6Be heated to 90～160 ℃ through preheater III, pressure 0.5～4.0MPa advances carbonyl synthesis reactor 8 oxo process dimethyl oxalates, the carbonyl synthesis reactor outlet material cools to 70～80 ℃ through interchanger IV, isolate most of dimethyl oxalate, the dimethyl oxalate burring acid esters dissolving tank 13 that condensation goes out.The exit gas of interchanger IV further absorbs dimethyl oxalate in the gas with methyl alcohol in dimethyl oxalate absorption tower 9,10～25 ℃ of absorption tower import methanol temperature, 50～70 ℃ of outlet methyl alcohol-dimethyl oxalate solution temperature, this solution can be used as the dimethyl oxalate hydrogenating materials after the degassing.
3, the regeneration of methyl nitrite: go out the gas on dimethyl oxalate absorption tower 9, press NO/O
2=4～8 volume ratios are replenished O
2After enter methyl nitrite regenerator column 10, regeneration flow into from cat head with methyl alcohol, 10～30 ℃ of temperature, methanol usage is pressed CH
3The mol ratio of OH/NO=1～3 adds, and the gas after the regeneration enters condenser VI at-30～10 ℃ of whole methyl nitrites that liquefy down behind condenser V condensation separation first alcohol and water, and the methyl nitrite of liquefaction enters methyl nitrite storage tank 11.Raffinate that evaporates in the isolated liquid of condenser, the methyl nitrite storage tank and methyl nitrite regenerator column outlet at bottom mass concentration arrive methanol rectifying tower 14 in the lump less than 50% methyl alcohol, obtain mass content after the rectifying greater than 70% thick methyl alcohol, the methyl nitrite regenerator column is removed in circulation.
4, dimethyl oxalate hydrogenation: the dimethyl oxalate methanol solution that comes out from dimethyl oxalate absorption tower 9 is made into the solution of mass concentration 50%～70% through outgasing with the dimethyl oxalate that comes from interchanger IV in dimethyl oxalate dissolving tank 13, send into preheater IX and H through volume pump
2Mix H
2Press H
2The molar ratio of/DMO=10～100 adds, and liquid air speed is in dimethyl oxalate 0.25～1, and gas temperature is 100～250 ℃ and removes hydrogenation synthesizer 16 after the preheating, and the temperature of hydrogenator is 180～240 ℃, pressure 0.5～4.0MPa.
5, the separation of hydrogenation products: dimethyl oxalate hydrogenator outlet product separates gas-liquid, isolated H through interchanger X cooling
2Hydrogenator is removed in circulation, and product liquid goes to the middle and lower part of pre-separation tower 17,63～75 ℃ of pre-separation column overhead temperature, and 140～170 ℃ of tower still temperature, cat head obtains methyl alcohol, and methyl alcohol returns the dimethyl oxalate synthesizing section; It is the mixing solutions of methyl glycolate and dimethyl oxalate that liquid is extracted at the tower middle part out, is ethylene glycol at the bottom of the tower.The mixing solutions of methyl glycolate and dimethyl oxalate goes to dibasic acid esters knockout tower 19 middle and lower parts, 141～152 ℃ of dibasic acid esters knockout tower tower top temperatures, overhead product is a methyl glycolate, tower still temperature is 155～165 ℃, bottom product is mainly dimethyl oxalate, dimethyl oxalate burring dimethyl phthalate dissolving tank 13.Dimethyl oxalate and methyl glycolate mixture also directly mix with dimethyl oxalate solution in the burring dimethyl phthalate dissolving tank 13.Pre-separation tower gained ethylene glycol removes the impurity of extraction tower 21 usefulness toluene, hexanaphthene extraction trace, goes ethylene glycol rectifying tower 22 to purify again and obtains polymerization-grade ethylene glycol.
6, vent gas treatment: the gas after the methyl nitrite regeneration does not coagulate gas through condenser V, and 90% gas that is recycled to molecular sieve dehydration tower 7,10% is pressed NO/O
2=4～8 volume ratios are joined oxygen and are removed tail gas absorber 12, the sodium carbonate solution of mass concentration 5%～20% flows into absorption of N O gas from the tail gas absorber cat head, obtain sodium nitrite solution, this solution is produced the mother liquor of Sodium Nitrite as raw material that NO takes place or work; Tail gas torch burning discharging after the processing.
But the steam of dehydrogenation reactor by-product 0.8～1.2Mpa in the said process can use for the alcohol ester knockout tower; But the steam of carbongl group synthesis reaction by-product 0.1～0.3Mpa can use for advancing the preceding preheater II of carbonyl synthesis reactor; But the steam of hydrogenator by-product 1.0～2.0Mpa can use for the dibasic acid esters knockout tower of back.
Following embodiment is the gas making raw material with coal, Sweet natural gas, residual oil respectively, adopts above-mentioned technical process to produce polymer grade ethylene glycol and co-producing methyl glycolate.
Embodiment 1
With the coal is the production technique of raw material:
Non-pressure process is the synthetic gas of raw material gas making preparation with the coal, and its volume percentage composition is 28% CO, 55% H
2, 10% N
2, 5%CO
2, 1% CH
4, 0.5% Ar, 0.2% O
2, water washing dedust, wet desulphurization, smart desulfurization remove organosulfur and the inorganic sulfur of the remnants in the source of the gas, make total sulfur content＜0.1 * 10
-6, remove transformation fractionation by adsorption CO and H then
2, the CO volume content after the separation is 98.5%, H
2Volume content is 99%; The burring dimethyl phthalate synthesizes and dimethyl oxalate hydrogenation workshop section respectively then.H among the CO
2Volume content is 1%, the oxygen of allocating 0.6% volume into goes the dehydrogenation reactor dehydrogenation, dehydrogenation catalyst is for being dissolved in 5 gram magnesium nitrates and 6 gram zinc nitrates in the 70 gram water, pour into then in the beaker that 100 gram alumina supporters are housed, the oven dry of dipping back, and in 450 ℃ of roastings 2 hours, then the carrier after the roasting is put into the mixing solutions 70 gram dipping absorption that are made into 0.6 gram Palladous chloride and 0.3 gram Platinic chloride, the dehydrogenation catalyst for feed gas containing carbon monoxide that makes after 480 ℃ of roastings, 130 ℃ of desorption temperatures, H in the CO source of the gas after the dehydrogenation
2Content is 20～60 * 10
-6, CO loss amount 0.2% arrives preheater then and mixes with methyl nitrite and circulation gas, and the percentage composition of gas mixture volume is 30% CO, 15% CH
3ONO, 5.5% NO, 45% N
2, 0.1% CH
3OH, 0.2% CO
2, 0.1% Ar, 0.19% CH4,0.01% H
2O, remove carbonyl synthesis reactor after the preheating, the carbongl group synthesis reaction catalyzer is for being dissolved in 15 gram ammonium molybdates and 10 gram ammonium paratungstates in 40 grams, 17% ammoniacal liquor, pour into then in the beaker that the long 8mm bar shaped of 100 gram diameter 3mm alpha-alumina supports is housed, the oven dry of dipping back, and in 550 ℃ of roastings 2 hours, then the carrier after the roasting is put into the 36g solution dipping Xi Fu Palladium that is made into 1.3 gram palladium, make the amount catalyzer, the carbongl group synthesis reaction temperature is 130 ℃, dimethyl oxalate purity 〉=99.5% of gained, CO selectivity 〉=99%, methyl nitrite transformation efficiency 〉=85%.Tail gas adopts the sodium carbonate solution of mass concentration 5% to join oxygen absorption, treats that the saturated back of absorption liquid is as the raw material that NO takes place.The dimethyl oxalate burring dimethyl phthalate hydrogenator hydrogenation reaction that synthesizes, hydrogenation catalyst is the 25%Cu/SiO of US5345005
2(quality percentage composition), 190～210 ℃ of hydrogenation reaction temperature, liquid air speed is 1h
-1, pressure 1.0MPa for obtaining more methyl glycolate, regulates H
2/ DMO is 40, liquid product mole percentage composition: 55% CH
3OH+1.2%DMO+10.45% MG+28% EG, dimethyl oxalate transformation efficiency 96%, selectivity 95% (MG+EG).Product is through pre-separation tower, alcohol ester knockout tower and obtain the methyl glycolate of purity 〉=99.5%, purity after the dibasic acid esters knockout tower separates〉98% ethylene glycol.Ethylene glycol removes extraction tower toluene extracting impurities, and rectification and purification obtains content in rectifying tower again〉99.9% polymerization-grade ethylene glycol.
Embodiment 2
With the Sweet natural gas is technique for producing raw material:
The Sweet natural gas pure oxygen transforms the synthetic gas of preparation, and its volume percentage composition is 26%CO, 60%H
2, 2%N
2, 10%CO
2, 1.5%CH
4, 0.4%Ar, 0.1%O
2, because the pre-treatment of Sweet natural gas process, raw material ratio is purer, after the smart desulfurization, directly removes transformation fractionation by adsorption CO and H
2, the CO volume content after the separation is 98.5%, H
2Volume content is 99%; The burring dimethyl phthalate synthesizes and dimethyl oxalate hydrogenation workshop section respectively then.H among the CO
2Volume content is 1.5%, the oxygen of allocating 0.9% volume into goes the dehydrogenation reactor dehydrogenation, dehydrogenation catalyst is for being dissolved in 3 gram iron nitrates, 10 gram ammonium meta-vanadates and 6 gram cerous nitrates in the 80 gram water, pour into then in the beaker that 100 gram alumina supporters are housed, the oven dry of dipping back, and in 100 ℃ of roastings 2 hours, then the carrier after the roasting is put into the 120 gram mixing solutions dipping absorption that are made into 0.5 gram Palladous chloride and 0.15 gram Platinic chloride, the dehydrogenation catalyst for feed gas containing carbon monoxide that makes after 800 ℃ of roastings, 180 ℃ of desorption temperatures, H in the CO source of the gas after the dehydrogenation
2Content is 80 * 10
-6, CO loss 0.24% is arrived preheater then and is mixed with methyl nitrite and circulation gas, and the percentage composition of mixed gas volume is 40%CO, 20%CH
3ONO, 10.5%NO, 25%N
2, 0.1%CH
3OH, 0.2%CO
2, 0.1%Ar, 0.19%CH
4, 0.01%H
2O, remove carbonyl synthesis reactor after the preheating, the carbongl group synthesis reaction catalyzer is for being dissolved in 15 gram iron nitrates and 10 gram manganous nitrates in the 45g water, pour into then in the beaker that 100 gram cloverleaf pattern alpha-alumina supports are housed, the oven dry of dipping back, and in 250 ℃ of roastings 2 hours, then the carrier after the roasting is put into the 37g mixing solutions dipping absorption palladium that is made into 0.25 gram Palladous chloride, the catalyzer that makes, the carbongl group synthesis reaction temperature is 100 ℃, dimethyl oxalate purity 〉=99.5% of gained, CO selectivity 〉=99%, methyl nitrite transformation efficiency 〉=80%.Tail gas adopts the sodium carbonate solution of mass concentration 20% to join oxygen absorption, treats that the saturated back of absorption liquid as the raw material of producing Sodium Nitrite, can get purity through the evaporation recrystallization〉98% Sodium Nitrite, can be used as commodity selling.The dimethyl oxalate that is synthesized goes the hydrogenator hydrogenation reaction, and hydrogenation catalyst is the 40%Cu-Cr of the clear 57-123127 of JP
2O
3(mass percentage concentration), 200～210 ℃ of hydrogenation reaction temperature, liquid air speed is 0.25h
-1, H
2/ DMO=80, pressure 3.0MPa, liquid product mole percentage composition: 55%CH
3OH+0.5%DMO+1.45%MG+36%EG, dimethyl oxalate transformation efficiency 99%, selectivity 97% (MG+EG).Hydrogenator comes out through condensed liquid product at alcohol ester knockout tower after separating, and all overhead products return the dimethyl oxalate dissolving tank.The purity that the alcohol ester knockout tower obtains is that 99% ethylene glycol removes extraction tower hexanaphthene extracting impurities, and rectification and purification obtains content in the ethylene glycol rectifying tower again〉99.9% polymerization-grade ethylene glycol.
Embodiment 3
With residual oil is technique for producing raw material:
The synthetic gas of long residuum gas making preparation, its volume percentage composition is 26%CO, 51%H
2, 12%N
2, 8%CO
2, 1%CH
4, 0.5%Ar, 0.2%O
2,, make total sulfur＜0.1 * 10 through taking off organosulfur and the inorganic sulfur that dirt, wet desulphurization, smart desulfurization remove the remnants in the source of the gas
-6, remove transformation fractionation by adsorption CO and H then
2, the CO volume content after the separation is 98.5%, H
2Volume content is 99%; The burring dimethyl phthalate synthesizes and dimethyl oxalate hydrogenation workshop section respectively then.H among the CO
2Content is 0.7%, the oxygen of allocating 0.45% volume into goes the dehydrogenation reactor dehydrogenation, dehydrogenation catalyst is for being dissolved in 5 gram SODIUMNITRATE, 10 gram iron nitrates and 10 gram manganous nitrates and 3 gram cerous nitrates in the 70 gram water, pour into then in the beaker that 100 gram alumina supporters are housed, the oven dry of dipping back, and in 450 ℃ of roastings 2 hours, then the carrier after the roasting is put into the 140 gram solution impregnation absorption that are made into 1 gram Palladous nitrate, the dehydrogenation catalyst for feed gas containing carbon monoxide that makes after 550 ℃ of roastings, 160 ℃ of desorption temperatures, H in the CO source of the gas after the dehydrogenation
2Content is 10～20 * 10
-6, CO loss 0.12% is arrived preheater then and is mixed with methyl nitrite and circulation gas, and the percentage composition of gas mixture volume is 20%CO, 10%CH
3ONO, 2.5%NO, 58%N
2, 0.1%CH
3OH, 0.2%CO
2, 0.1%Ar, 0.19%CH
4, 0.01%H
2O, remove carbonyl synthesis reactor after the preheating, the carbongl group synthesis reaction catalyzer is for being dissolved in 5 gram magnesium nitrates and 6 gram zinc nitrates in the 30g water, pour into then in the beaker that the spherical alpha-alumina supports of 100 gram diameter 4mm is housed, the oven dry of dipping back, and in 650 ℃ of roastings 2 hours, then the carrier after the roasting is put into the 28g solution dipping absorption palladium that is made into 0.6 gram Palladous chloride, this catalyzer that makes, the carbongl group synthesis reaction temperature is 120 ℃, dimethyl oxalate purity 〉=99.5% of gained, CO selectivity 〉=99%, methyl nitrite transformation efficiency 〉=90%.Tail gas adopts the sodium carbonate solution of mass concentration 15% to join oxygen absorption, treats that the saturated back of absorption liquid is as the raw material that NO takes place.The dimethyl oxalate that synthesizes goes the hydrogenator hydrogenation reaction, and hydrogenation catalyst is commercial methanol catalyzer C307,200～210 ℃ of hydrogenation reaction temperature, and liquid air speed is 0.8h
-1, H
2/ DMO=80, pressure 2.0MPa, liquid product mole percentage composition: 55%CH
3OH+2.5%DMO+5.45%MG+32%EG, dimethyl oxalate transformation efficiency 91%, selectivity 92% (MG+EG).Product is through pre-separation tower, alcohol ester knockout tower and obtain the methyl glycolate purity of purity 〉=99.5% after the dibasic acid esters knockout tower separates〉98% ethylene glycol.Ethylene glycol removes extraction tower toluene extracting impurities, and rectification and purification obtains content in the ethylene glycol rectifying tower again〉99.9% polymerization-grade ethylene glycol.
The polymerization-grade ethylene glycol of embodiment 1,2,3 gained meets the requirement of the excellent industrial goods of ethylene glycol fully, and analytical results sees Table 2:
The industrial ethylene glycol of table 1 GB/T4649-2008
The ethylene glycol analytical results that three embodiment of table 2 obtain
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Outward appearance | Water white transparency does not have mechanical impurity | Water white transparency does not have mechanical impurity | Water white transparency does not have mechanical impurity |
| Quality of glycol mark/% | 99.94 | 99.91 | 99.95 |
| After adding the hydrochloric acid heating before colourity (platinum-cobalt)/number heating | 4 16 | 5 19 | 4 15 |
| Density (20 ℃)/(g/cm 3) | 1.1129 | 1.1136 | 1.1131 |
| Boiling range (0 ℃, 0.10133Mpa) initial boiling point/℃ final boiling point/℃ | 196.8 197.9 | 196.6 198.1 | 196.9 197.7 |
| Moisture (massfraction)/% | 0.02 | 0.05 | 0.01 |
| Acidity (with acetometer)/% | 0.0003 | 0.0005 | 0.0002 |
| Iron (massfraction)/% | 0.000002 | 0.000006 | 0.000003 |
| Ash content (massfraction)/% | 0.0002 | 0.0004 | 0.001 |
| Diethylene Glycol (massfraction)/% | 0.004 | 0.008 | 0.002 |
| Aldehyde massfraction (in formaldehyde)/% | 0.0003 | 0.0005 | 0.0002 |
| During ultraviolet transmittance/% 220nm during 275nm during 350nm | 81 94 99.7 | 79 95 99.5 | 84 97 99.8 |
Claims (9)
1, a kind of method of producing polymer grade ethylene glycol and co-producing methyl glycolate: it is characterized in that, be the unstripped gas that raw material makes with coal, Sweet natural gas or residual oil, through dedusting, wet desulphurization, decarburization, the absorption of PSA transformation and smart desulfurization, isolates CO and H
2, isolated CO is under the participation of methyl nitrite, by the Pd/ α-Al of two kinds of auxiliary agents of a kind of interpolation
2O
3The catalyzer oxo process is produced dimethyl oxalate, and product obtains highly purified dimethyl oxalate through separation, and tail gas is through the nitrosification recycling utilization; The dimethyl oxalate that obtains is at a kind of Cu-SiO
2Or Cu-Cr
2O
3Or the catalysis of Cu-Zn-Al catalyst for methanol is following and H
2Reaction obtains ethylene glycol and methyl glycolate, and product obtains ethylene glycol and methyl glycolate through extraction, rectifying separation, regulates the fractional yield that working condition changes ethylene glycol and methyl glycolate.
2, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1 is characterized in that: described unstripped gas is isolated CO and H through dedusting, wet desulphurization, decarburization, the absorption of PSA transformation and smart desulfurization
2, make total sulfur＜0.1ppm among the CO, CO purity 〉=98.5%; H
2Middle total sulfur＜0.1ppm, H
2Purity 〉=99%.
3, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1 is characterized in that: contain 0.1%-1.5%H in the CO gas that described PSA transformation fractionation by adsorption goes out
2Adopt the oxygenation catalytic eliminating, dehydrogenation catalyst be a kind of be carrier with the aluminum oxide, palladium and/or platinum are active ingredient, and 2-4 kind MOx is an auxiliary agent, and M is the catalyzer of sodium, potassium, magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten or cerium, the composition of catalyzer is counted with the carrier quality: palladium 0.01%～2% and platinum 0.01%～1%, perhaps palladium 0.01%～2% or platinum 0.01%～1%, the total amount of 2-4 kind MOx is 1%～20%, H in the CO gas after the catalytic dehydrogenation
2＜100 * 10
-6, O
2＜1000 * 10
-6, the loss amount of CO＜0.3%.
4, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1, it is characterized in that: after the CO that described PSA transformation fractionation by adsorption goes out removes hydrogen, carry out carbongl group synthesis reaction with methyl nitrite, at the Pd/ α-Al of two kinds of auxiliary agents of a kind of interpolation
2O
3Synthesizing dimethyl oxalate on the catalyzer, this catalyzer is carrier with the Alpha-alumina, palladium is an active ingredient, 2 kinds of MOx are auxiliary agent, M is magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, copper, zinc, molybdenum or tungsten, the composition of catalyzer is counted with the carrier quality: palladium 0.01%～0.75%, the total amount of 2 kinds of MOx are 0.1%～20%, the selectivity of dimethyl oxalate synthetic catalyst〉99%.
5, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1, it is characterized in that: the gas cooling that carbongl group synthesis reaction comes out is to 70-80 ℃, isolate most dimethyl oxalate product, this product further cooling obtains highly purified dimethyl oxalate product, purity〉99.5%.
6, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1 is characterized in that: described methyl nitrite adopts NO, methyl alcohol and purity〉90% industrial oxygen reaction makes, and presses NO/O
2=4～8 mol ratio is mended into industrial oxygen, presses CH
3The mol ratio of OH/NO=1～3 adds methyl alcohol, and controlled temperature makes above-mentioned being reflected under the gas phase condition carry out product C H
3ONO adopts the pressurization condensation separation.
7, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1 is characterized in that: CH, take place through the nitrosification reprocessing cycle in the tail gas after coming out after the dimethyl oxalate that carbongl group synthesis reaction produces separates
3ONO, the CO recycle, tail gas and industrial oxygen that part contains NO enter tail gas absorber at the bottom of tower, use the sodium carbonate solution of mass concentration 5%-20% to add absorption of N O from cat head, the torch burning emptying of reducing internal heat of other gases, the Sodium Nitrite that from absorption liquid, obtains or the NO recycle takes place.
8, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 1 is characterized in that: the product that oxo process is produced, the high-purity oxalic acid dimethyl ester that obtains through condensation separation is with H
2Press H
2/ dimethyl oxalate=10～100 mol ratios enter hydrogenator, a kind of Cu-SiO of filling in the hydrogenator
2Or Cu-Cr
2O
3Or the Cu-Zn-Al catalyst for methanol, the hydrogenator inlet temperature is 100～250 ℃, pressure 0.5～4MPa hydrogenation reaction product is mainly ethylene glycol and methyl glycolate, and ethanol, butyleneglycol, methylcarbonate, aldehydes and ketone by product are perhaps arranged simultaneously.
9, the method for production ethylene glycol with coproduction product methyl glycolate according to claim 8 is characterized in that: the H that regulates hydrogenation reaction
2/ dimethyl oxalate mol ratio, temperature and air speed condition can change the ratio of glycol product and methyl glycolate.
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