CN104496755A - Purification process for preparing raw material methanol in gasoline through methanol conversion - Google Patents
Purification process for preparing raw material methanol in gasoline through methanol conversion Download PDFInfo
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Abstract
The invention discloses a purification process for preparing a raw material methanol in gasoline through methanol conversion. The purification process comprises the steps of filling an acidic resin into a 1# purification tower and a 2# purification tower respectively, and preprocessing with desalted water and diluted hydrochloric acid solution; when the acidic nitrogen content in the raw material methanol is lower than 700ppm, feeding the raw material methanol into the 1# purification tower and/or the 2# purification tower for purification, feeding the raw material methanol into a pre-purification tower for pre-purification when the basic nitrogen content in the raw material methanol exceeds 700ppm, and then feeding into the 1# purification tower or the 2# purification tower when the basic nitrogen content in the raw material methanol is lower than 700ppm. The purification process provided by the invention has the advantages of being simple in flow and good in purification effect.
Description
Technical field
The invention belongs to a kind of purification process of methanol conversion gasoline Raw methyl alcohol.
Technical background
China has the energy structure of rich coal, oil-poor and weak breath, and especially the imbalance between supply and demand of oil is day by day serious.Coal liquifaction technology meets the adjustment direction of China's energy structure, is to alleviate the most effective approach of petroleum-based energy shortage problem.Coal liquifaction technology is divided into direct liquefaction and indirect liquefaction, wherein indirect liquefaction comprises Fischer-Tropsch (F-T) synthesis and preparing gasoline by methanol (MTG) two kinds of technology, compare with ICL for Indirect Coal Liquefaction F-T synthetic technology with DCL/Direct coal liquefaction, preparing gasoline by methanol have that technique is simple, the reliable and yield of gasoline advantages of higher of technology maturation.Consider developing rapidly of Chemical Industry in recent years simultaneously, make ammonia from coal problem of excess production capacity day by day serious.Therefore, the successful exploitation of technique for preparing gasoline by methanol and industrial applications not only alleviate the problem such as domestic petroleum shortage and methyl alcohol surplus, and have enriched the technological line of coal, have important practical significance.
At present, the fixed bed one step method MTG technique that the fixed bed two-step approach MTG technique of industrial main employing american exxon-Mobil Corp. exploitation and SaiDing Engineering Co., Ltd and coalification are developed cooperatively.The former be first by methyl alcohol at Cu/Al
2o
3on catalyzer, dehydration forms dme, then dme is converted into high-octane gasoline products under the katalysis of ZSM-5; And the latter is methyl alcohol is converted into gasoline products on modified zsm-5 zeolite.Acid sites in ZSM-5 catalyzer is the chief active position of methanol conversion, and space constraint effect can be played in intersection two ducts of catalyzer uniqueness, controls gasoline products at below C11.But molecular sieve pore passage structure is narrower and long, easily cause reactant and product long-time delay and the generation that causes carbon distribution to react in duct, further blocking diffusion admittance and covering active centre make catalyst deactivation, the carbon distribution inactivation of catalyzer belongs to renewable inactivation, can be recovered the activity of catalyzer by the oxygen combustion in air.
At present, industry MTG device building-up reactions generally runs 15 ~ 20 days rear catalysts will carbon distribution inactivation, MTG catalyst regeneration 14 ~ 17 all after dates under normal circumstances, catalyzer owing to there occurs efflorescence, duct caves in and the irreversible inactivation such as acid loss and changing, its total treatment capacity reaches 8000 ~ 10000 tons of methyl alcohol/ton catalyzer.But often can run into live catalyst filling in process of production in the near future can fast deactivation; separate run times is only 6 ~ 7 days just needs regeneration afterwards; the total treatment capacity of catalyzer is only after 3000 ~ 5000 tons of methyl alcohol/ton catalyzer must more catalyst changeout; not only increase investment and the running cost of catalyzer; and had a strong impact on normally carrying out of production, become numerous MTG producers urgent need to solve the problem.
SaiDing Engineering Co., Ltd and Inner Mongol Qing Hua group are on the MTG device of second phase 100,000 tons/year, by more catalyst changeout, adjustment working condition, optimize regeneration condition and change the series of measures such as methyl alcohol starting material and the problems referred to above are analyzed and investigates, find catalyzer, working condition and regeneration condition are less to the stability influence produced, and have affect more significantly by changing the stability of methanol feedstock on catalyzer, catalyst characterization after inactivation is found simultaneously, catalyzer after inactivation does not find the phenomenon of caving in of efflorescence and pore passage structure, but it is very fast to find that the acid amount of catalyzer runs off.The above analysis is known, causes the major cause of rapid catalyst deactivation to be that this impurity can cause the loss in acidity of catalyst active centre, and then causes the non-renewable inactivation of catalyzer containing certain impurity in methanol feedstock.Therefore, develop a kind of purification process of MTG charging methyl alcohol, be solve the improper inactivation of MTG catalyzer, ensure the most effective approach of the steady running of producing.
Summary of the invention
The object of the invention is the improper deactivation phenomenom for catalyzer in MTG production process, and it is simple to develop a kind of flow process, the purification process of the methanol conversion gasoline Raw methyl alcohol of good purification.
The present invention effectively eliminates the impurity in methanol feedstock, not only solves the improper deactivation prob of catalyzer, and extends the one way working time of catalyzer further, adds the entire life of number of run and catalyzer.
For reaching above-mentioned purpose, first contriver analyzes the methyl alcohol from different manufacturer, find that in the methyl alcohol that different manufacturers is produced, dopant species reaches kind more than 20, and its content is with methyl alcohol source and batch different generation fluctuation on a large scale, then according to the detection level of impurity in methanol feedstock, by the simultaneous test of the methanol feedstock and pure methanol feedstock of allocating single impurity into is found, ammonia, methylamine, the introducing of the basic nitrogen impurities such as dimethylamine and Trimethylamine 99 can cause rapidly the inactivation of catalyzer, and the major cause of its inactivation is the loss in acid active centre in catalyzer, this is due to the aobvious alkalescence of basic nitrogen compound, it understands the acid sites generation chemisorption with catalyzer, because this chemisorption intensity is higher, and be difficult to desorption by conventional method, and then cause rapid catalyst deactivation.
Basic nitrogen class impurity according to containing in the methyl alcohol obtained above is the major cause causing the improper inactivation of MTG catalyzer, we analyze the content of the basic nitrogen in methanol feedstock emphatically, find that the content difference of different methanol feedstock neutral and alkali nitrogen is huge, its content range is 100 ~ 1000ppm, wherein when basic n content is 1000ppm, fast deactivation after catalyzer single in industrial methanol production equipment runs 7 days, continues through above-mentioned methanol feedstock 30 days thorough inactivations of rear catalyst.We have studied basic n content further by a large amount of lab scales and sideline test affects catalyst stability, find when methyl alcohol neutral and alkali nitrogen content is lower than 40ppm, catalyst stability is good, and when its content is higher than 40ppm, catalyst deactivation is very fast, normally runs working time and entire life lower than catalyzer.But consider that the impact of basic nitrogen on catalyzer is non-renewable, determine basic n content to control at below 20ppm according to knowhow for many years.
The technology removing basic nitrogen mainly contains salt pickling, liquid-solid absorption method and complexometry three class, contriver is according to many factors such as technical stability, cost of investment, running cost and removal effects, and the through engineering approaches experience combined for many years selects acidic ion exchange resin removing sulfuldioxide, further by a large amount of sideline test, have selected kind and the operational condition of resin.When carrying out purification process design, considering that the basic n content variation range in methanol feedstock is very big, needing the purification of multistage resin when basic n content is high; And resin is expensive, when single scavenging tower go out rear methyl alcohol neutral and alkali nitrogen slightly exceed standard time, in its scavenging tower, the decontamination effect improving of resin does not have completely dissolve.Consider above-mentioned factor, contriver is according to sideline test, and the knowhow of the MTG engineering design combined for many years and MTG, develop a kind of three tower purification process, one of them is preliminary cleaning tower, and another two is scavenging tower; When the content in material benzenemethanol is lower, methanol feedstock purifies by means of only a tower, and all the other two towers are in stand-by state, when the methyl alcohol neutral and alkali nitrogen content after a scavenging tower purification exceeds standard, switching two scavenging tower is series connection, making the scavenging tower purification of material benzenemethanol first through exceeding standard, purifying through new scavenging tower; And when methanol feedstock neutral and alkali nitrogen content is high, then open preliminary cleaning tower, make material benzenemethanol first by after the purification of preliminary cleaning tower, purified by two scavenging tower.Above-mentioned technique not only can fluctuate under great operating mode and effectively purifies material benzenemethanol by methanol feedstock neutral and alkali nitrogen content, and the effect of acidic ion exchange resin can be made full use of, extend MTG working time and entire life, there is important theory and realistic meaning.
A kind of purification process for methanol conversion gasoline Raw methyl alcohol disclosed by the invention comprises the steps:
(1) acidic resins are loaded into preliminary cleaning tower respectively, in 1# scavenging tower and 2# scavenging tower, first salt solution is conveyed into preliminary cleaning tower from top, in 1# scavenging tower and 2# scavenging tower, after soaking resin certain hour, salt solution is put only, and by de-salted water by the resin rinsed clean in scavenging tower, then dilute hydrochloric acid solution is conveyed in three scavenging tower from top, after soaking resin certain hour, hydrochloric acid soln is put only, and by de-salted water by the resin rinsed clean in scavenging tower, finally purging nitrogen is sent in three scavenging tower from top, free-water in resin is purged totally, complete the pre-treatment of resin,
(2) after resin pre-treatment completes, when the basic n content in material benzenemethanol is lower than 700ppm, sent in 1# scavenging tower from top by material benzenemethanol and purify, preliminary cleaning tower and 2# scavenging tower are in stand-by state, and the methyl alcohol after the purification of scavenging tower 1# tower is sent to synthetic oil system;
(3) along with the carrying out of material benzenemethanol purification, when detecting 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides more than 20ppm, methyl alcohol is made first to carry out primary purification through 1# scavenging tower, material benzenemethanol after primary purification is sent to 2# scavenging tower again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system;
(4) when detecting that the decontamination effect improving of 1# scavenging tower reaches the low point value of setting, then stop the charging of 1# scavenging tower, whole charging methyl alcohol is all purified by 2# scavenging tower, methyl alcohol after purification is sent to synthetic oil system, carry out the replacing of acidic ion exchange resin in 1# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 1# scavenging tower, and be in stand-by state;
(5) when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, material benzenemethanol is then made first to carry out primary purification through 2# scavenging tower, material benzenemethanol after primary purification is sent to 1# scavenging tower again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system;
(6) when detecting that the decontamination effect improving of 2# scavenging tower reaches the low point value of setting, then stop the charging of 2# scavenging tower, whole material benzenemethanol all enters 1# scavenging tower and purifies, methyl alcohol after purification is sent to synthetic oil system, carry out the replacing of acidic ion exchange resin in 1# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 1# scavenging tower, and be in stand-by state;
(7) repeating step (2) ~ (6) then can realize the continuous purification operation of the methyl alcohol as methyl alcohol neutral and alkali nitrogen content≤700ppm;
(8) carry out in process in purification, when the basic n content in material benzenemethanol being detected more than 700ppm, first material benzenemethanol is sent in preliminary cleaning tower from top and carries out preliminary cleaning, methyl alcohol neutral and alkali amount of nitrides after preliminary cleaning is lower than 700ppm, and then be sent in 1# scavenging tower or 2# scavenging tower, and repeating step (2) ~ (6) purify again, and after material benzenemethanol neutral and alkali nitrogen content is lower than 700ppm, then close charging and the discharge valve of preliminary cleaning tower, make it still be in stand-by state.
As above is saturated aqueous common salt for the pretreated salt solution of resin, and soak time is 15 ~ 24h.
Mass concentration as above for the pretreated dilute hydrochloric acid solution of resin is 1 ~ 8wt%, and its soak time is 2 ~ 10h.
The feeding temperature of material benzenemethanol as above is 20 ~ 60 DEG C, and optimum is 30 ~ 50 DEG C.
The acidic resins loaded in preliminary cleaning tower as above, 1# scavenging tower and 2# scavenging tower are CT151 type or the C100E type of drift Lai Te (China) company; The D113 type that Chemical Plant of Nankai Univ. produces, D061 type or D152 type.
In scavenging tower as above, the granularity of acidic resins is 0.5 ~ 1.5mm, and its coefficient of uniformity is 1.5 ~ 2.
Methyl alcohol as above is 1 ~ 30h through the mass space velocity that acidic resins exchange
-1, more excellent is 10 ~ 20h
-1.
The low point value of scavenging tower decontamination effect improving setting as above, namely judges decreasing ratio≤20% of foundation as methyl alcohol neutral and alkali nitride of acidic resins inefficacy in scavenging tower.
Methyl alcohol neutral and alkali nitrogen removal efficiency as above after scavenging tower purification reaches 94 ~ 99%, and outlet methyl alcohol neutral and alkali nitrogen content is less than or equal to 20ppm.
The present invention compared with prior art, has substantive distinguishing features and marked improvement is:
(1) the present invention analyzes running into the improper inactivation of catalyzer in MTG production, and give concrete purification process and working method, not only solve the improper deactivation phenomenom run in preparing gasoline by methanol, and after increasing purification process of the present invention, catalyzer one way extended to 21 ~ 28 days by 15 ~ 20 days working time, the regeneration period of catalyzer is increased to more than 18 times by 11 ~ 16 times, the total treatment capacity of catalyzer adds nearly 20%, substantially increases stability and the economic benefit of MTG production.
(2) the present invention proposes methanol purification technique and working method is provided with two scavenging tower, when one of them scavenging tower outlet methyl alcohol exceeds standard, by this scavenging tower outlet methyl alcohol is entered another scavenging tower, not only ensure that removal effect, and the effect of acidic ion exchange resin is not fully exerted, save investment.
(3) the present invention proposes methanol purification technique before two scavenging tower, be also provided with a preliminary cleaning tower, when charging methyl alcohol neutral and alkali nitrogen content is higher, can by material benzenemethanol newly by the preliminary cleaning of preliminary cleaning tower, make the methyl alcohol neutral and alkali nitrogen content of preliminary cleaning lower than after 700ppm, purifying through follow-up two scavenging tower, the purity of scavenging tower outlet methyl alcohol when ensure that charging methyl alcohol neutral and alkali nitrogen content is higher.
Accompanying drawing explanation
Fig. 1 is a kind of purification process figure for methanol conversion gasoline Raw methyl alcohol disclosed by the invention
As shown in the figure, technique comprises preliminary cleaning tower, 1# scavenging tower and 2# scavenging tower, P1, P2, P3a, P3b, P4, P5, P6a, P6b, P7a, P7b and P8 are pipeline, and V1, V2, V3a, V3b, V3c, V4, V5, V6a, V6b, V7a, V7b, V8a, V8b, V9a, V9b, V10a, V10b, V11a, V11b and V11c are valve.
A kind of purification process for methanol conversion gasoline Raw methyl alcohol disclosed by the invention, can by reference to the accompanying drawings 1, undertaken further by following working method:
(1) acidic resins are loaded into preliminary cleaning tower, in 1# scavenging tower and 2# scavenging tower, open valve V2, V3a, V3b and V3c, and remaining pipes valve closes, first salt solution is sent into preliminary cleaning tower through pipeline P2 from top, in 1# scavenging tower and 2# scavenging tower, after soaking resin certain hour, open valve V11a, V11b and V11c, salt solution is sent to water treatment system through pipeline P5, by de-salted water to the resin rinsed clean in scavenging tower, valve-off V11a, V11b and V11c, and then dilute hydrochloric acid solution is sent into preliminary cleaning tower through pipeline P2, in 1# scavenging tower and 2# scavenging tower, after soaking resin certain hour, open valve V11a, V11b and V11c, hydrochloric acid soln is put only, and by de-salted water by the resin rinsed clean in scavenging tower, then purging nitrogen to be sent in three scavenging tower from top by pipeline P2 and resin is purged, the water purged out is sent to water treatment system through P5, purge totally until the free-water in resin, complete the pre-treatment of resin.
(2) when the basic n content in material benzenemethanol is lower than 700ppm, open valve V1, V6a, V7a, V10a, V9a, all the other valve closess, material benzenemethanol purifies in the feeding 1# scavenging tower of top through pipeline P1 and P3a, methyl alcohol after purification is sent to system for methanol synthesis through pipeline P6a and P8, and preliminary cleaning tower and 2# scavenging tower are in stand-by state.
(3) along with the carrying out of methanol purification, when detecting 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides more than 20ppm, then valve-off V9a, and open valve V8b, V7b, V10b and V9b, make methyl alcohol first send into 1# scavenging tower through pipeline P1 and P3a from top and carry out primary purification, methyl alcohol after primary purification is sent to 2# scavenging tower by pipeline P6a, P7b and P3b again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system through pipeline P6b and P8.
(4) when detecting that the decontamination effect improving of 1# scavenging tower reaches the low point value of setting, then valve-off V6a, V7a, V10a, V8b, and open valve V6b, whole material benzenemethanol is all sent into 2# scavenging tower by pipeline P1 and P3b from top and is purified, methyl alcohol after purification is sent to synthetic oil system through pipeline P6b and P8, carry out the replacing of acidic ion exchange resin in 1# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 1# scavenging tower, be in stand-by state after pre-treatment completes.
(5) when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then valve-off V9b, and open valve V8a, V7a, V10a, V9a, make methyl alcohol first send into 2# scavenging tower through pipeline P1 and P3b from top and carry out primary purification, methyl alcohol after primary purification is sent to 2# scavenging tower by pipeline P6b, P7a and P3a again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system through pipeline P6a and P8.
(6) when detecting that the decontamination effect improving of 2# scavenging tower reaches the low point value of setting, then valve-off V6b, V7b, V10b, V8a, and open valve V6a, whole charging methyl alcohol is all sent into 1# scavenging tower by pipeline P1 and P3a from top and is purified, methyl alcohol after purification is sent to synthetic oil system through pipeline P6a and P8, carry out the replacing of acidic ion exchange resin in 2# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 2# scavenging tower, be in stand-by state after pre-treatment completes.
(7) repeating step (2) ~ (6) then can realize the continuous purification operation of the methyl alcohol as methyl alcohol neutral and alkali nitrogen content≤700ppm.
(8) carry out in process in purification, when the basic n content in material benzenemethanol being detected more than 700ppm, then open valve V4 and V5, valve-off V1 and V11a, first material benzenemethanol is sent in preliminary cleaning tower from top and carries out preliminary cleaning, methyl alcohol neutral and alkali amount of nitrides after preliminary cleaning is lower than 700ppm, then be sent in 1# or 2# scavenging tower through pipeline P4 and P1, and repeating step (2) ~ (6) purify again, methyl alcohol after purifying again is sent to synthetic oil system, and after methanol feedstock neutral and alkali nitrogen content is lower than 700ppm, then valve-off V4, V5 and V11a, it is made still to be in stand-by state.
Embodiment
Below by specific embodiment, the specific embodiment of the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to above-described embodiment.
Embodiment 1
The present embodiment adopts the methyl alcohol containing basic nitrogen 600ppm as scavenging tower charging, and the cleansing operation step of its concrete methanol feeding is as follows:
(1) by 0.5 ~ 1.5mm, uniformity ratio be 1.5 drift Lai Te (China) company CT151 type acidic resins be loaded into preliminary cleaning tower, in 1# scavenging tower and 2# scavenging tower, open valve V2, V3a, V3b and V3c, and remaining pipes valve closes, first saturated aqueous common salt is sent into preliminary cleaning tower through pipeline P2 from top, in 1# scavenging tower and 2# scavenging tower, after soaking resin 15h, open valve V11a, V11b and V11c, salt solution is sent to water treatment system through pipeline P5, by de-salted water to the resin rinsed clean in scavenging tower, valve-off V11a, V11b and V11c, and then be that the dilute hydrochloric acid solution of 1wt% sends into preliminary cleaning tower through pipeline P2 by mass concentration, in 1# scavenging tower and 2# scavenging tower, after soaking resin 10h, open valve V11a, V11b and V11c, hydrochloric acid soln is put only, and by de-salted water by the resin rinsed clean in scavenging tower, then purging nitrogen to be sent in two scavenging tower from top by pipeline P2 and resin is purged, the water purged out is sent to water treatment system through P15, purge totally until the free-water in resin, complete the pre-treatment of resin.
(2) open valve V1, V6a, V7a, V10a, V9a, all the other valve closess, being that the material benzenemethanol of 20 DEG C purifies in the feeding 1# scavenging tower of top through pipeline P1 and P3a by temperature, is 5h at mass space velocity
-1purify, the methyl alcohol after purification is sent to system for methanol synthesis through pipeline P6a and P8, and preliminary cleaning tower and 2# scavenging tower are in stand-by state.
(3) along with the carrying out of material benzenemethanol purification, when detecting 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides more than 20ppm, then valve-off V9a, and open valve V8b, V7b, V10b and V9b, make methyl alcohol first send into 1# scavenging tower through pipeline P1 and P3a from top and carry out primary purification, methyl alcohol after primary purification is sent to 2# scavenging tower by pipeline P6a, P7b and P3b again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system through pipeline P6b and P8.
(4) when detecting that the decontamination effect improving of 1# scavenging tower reaches the low point value of setting, i.e. decreasing ratio≤20% of methyl alcohol neutral and alkali nitride, then valve-off V6a, V7a, V10a, V8b, and open valve V6b, whole material benzenemethanol is all sent into 2# scavenging tower by pipeline P1 and P3b from top and is purified, methyl alcohol after purification is sent to synthetic oil system through pipeline P6b and P8, carry out the replacing of acidic ion exchange resin in 1# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 1# scavenging tower, stand-by state is in after pre-treatment completes.
(5) when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then valve-off V9b, and open valve V8a, V7a, V10a, V9a, make material benzenemethanol first send into 2# scavenging tower through pipeline P1 and P3b from top and carry out primary purification, methyl alcohol after primary purification is sent to 2# scavenging tower by pipeline P6b, P7a and P3a again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system through pipeline P6a and P8.
(6) when detecting that the decontamination effect improving of 2# scavenging tower reaches the low point value of setting, i.e. decreasing ratio≤20% of methyl alcohol neutral and alkali nitride, then valve-off V6b, V7b, V10b, V8a, and open valve V6a, whole material benzenemethanol is all sent into 1# scavenging tower by pipeline P1 and P3a from top and is purified, methyl alcohol after purification is sent to synthetic oil system through pipeline P6a and P8, carry out the replacing of acidic ion exchange resin in 2# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 2# scavenging tower, stand-by state is in after pre-treatment completes.
(7) repeating step (2) ~ (6) then can realize the continuous purification operation of material benzenemethanol.
Under the operation steps and operational condition of the present embodiment, basic nitrogen decreasing ratio in its methyl alcohol is 98%, the content of outlet basic nitrogen compound is 12 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 25 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 13500 tons of methyl alcohol/ton catalyzer.
Embodiment 2
The present embodiment adopts the methyl alcohol containing basic nitrogen 1000ppm as scavenging tower charging, step (1) in the pre-treatment step detailed in Example 1 of its resin, open valve V4 and V5, valve-off V1 and V11a, first material benzenemethanol is sent in preliminary cleaning tower from top and carries out preliminary cleaning, methyl alcohol neutral and alkali amount of nitrides after preliminary cleaning is lower than 700ppm, then be sent in 1# or 2# scavenging tower through pipeline P4 and P1, and repeat embodiment 1 step (2) ~ (6) and purify again, methyl alcohol through purifying again is sent to synthetic oil system, and its operational condition is as follows:
Drift Lai Te (China) the company C100E type acidic resins that employing granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.6, saturated common salt water soaking resin 18h, mass concentration is that 2wt% dilute hydrochloric acid solution soaks resin 9h, and material benzenemethanol inlet temperature is 30 DEG C, and the mass space velocity of its purification is 1h
-1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen decreasing ratio in its methyl alcohol is 98%, outlet basic nitrogen compound content is 7 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 22 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 11880 tons of methyl alcohol/ton catalyzer.
Embodiment 3
The present embodiment adopts the methyl alcohol containing basic nitrogen 300ppm as scavenging tower charging, the D113 type resin that Chemical Plant of Nankai Univ. that employing granularity is granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.8 produces, saturated common salt water soaking resin 20h, mass concentration is that 4wt% dilute hydrochloric acid solution soaks resin 9h, material benzenemethanol inlet temperature is 40 DEG C, and the mass space velocity of its purification is 13h
-1, all the other are with embodiment 1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen decreasing ratio in its methyl alcohol is 96%, outlet basic nitrogen compound content is 16 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 27 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 14580 tons of methyl alcohol/ton catalyzer.
Embodiment 4
The present embodiment adopts the methyl alcohol containing basic nitrogen 200ppm as scavenging tower charging, the D061 type resin that Chemical Plant of Nankai Univ. that employing granularity is granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.9 produces, saturated common salt water soaking resin 22h, mass concentration is that 7wt% dilute hydrochloric acid solution soaks resin 5h, material benzenemethanol inlet temperature is 50 DEG C, and the mass space velocity of its purification is 25h
-1, all the other are with embodiment 1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen decreasing ratio in its methyl alcohol is 95%, outlet basic nitrogen compound content is 10 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the GSK-10 type MTG catalyzer of rope company of Top exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 26 days, the regeneration period 19 times, the total treatment capacity of unit catalyst 14820 tons of methyl alcohol/ton catalyzer.
Embodiment 5
The present embodiment adopts the methyl alcohol containing basic nitrogen 100ppm as scavenging tower charging, the D152 type resin that Chemical Plant of Nankai Univ. that employing granularity is granularity is 0.5 ~ 1.5mm, uniformity ratio is 2.0 produces, saturated common salt water soaking resin 24h, mass concentration is that 7wt% dilute hydrochloric acid solution soaks resin 2h, material benzenemethanol inlet temperature is 60 DEG C, and the mass space velocity of its purification is 30h
-1, all the other are with embodiment 1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen decreasing ratio in its methyl alcohol is 94%, outlet basic nitrogen compound content is 6 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the GSK-10 type MTG catalyzer of rope company of Top exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 28 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 14460 tons of methyl alcohol/ton catalyzer.
Claims (13)
1., for a purification process for methanol conversion gasoline Raw methyl alcohol, it is characterized in that comprising the steps:
(1) acidic resins are loaded into preliminary cleaning tower respectively, in 1# scavenging tower and 2# scavenging tower, first salt solution is conveyed into preliminary cleaning tower from top, in 1# scavenging tower and 2# scavenging tower, after soaking resin certain hour, salt solution is put only, and by de-salted water by the resin rinsed clean in scavenging tower, then dilute hydrochloric acid solution is conveyed in three scavenging tower from top, after soaking resin certain hour, hydrochloric acid soln is put only, and by de-salted water by the resin rinsed clean in scavenging tower, finally purging nitrogen is sent in three scavenging tower from top, free-water in resin is purged totally, complete the pre-treatment of resin,
(2) after resin pre-treatment completes, when the basic n content in material benzenemethanol is lower than 700ppm, sent in 1# scavenging tower from top by material benzenemethanol and purify, preliminary cleaning tower and 2# scavenging tower are in stand-by state, and the methyl alcohol after the purification of scavenging tower 1# tower is sent to synthetic oil system;
(3) along with the carrying out of material benzenemethanol purification, when detecting 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides more than 20ppm, methyl alcohol is made first to carry out primary purification through 1# scavenging tower, material benzenemethanol after primary purification is sent to 2# scavenging tower again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system;
(4) when detecting that the decontamination effect improving of 1# scavenging tower reaches the low point value of setting, then stop the charging of 1# scavenging tower, whole charging methyl alcohol is all purified by 2# scavenging tower, methyl alcohol after purification is sent to synthetic oil system, carry out the replacing of acidic ion exchange resin in 1# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 1# scavenging tower, and be in stand-by state;
(5) when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, material benzenemethanol is then made first to carry out primary purification through 2# scavenging tower, material benzenemethanol after primary purification is sent to 1# scavenging tower again and carries out secondary-cleaned, and the methyl alcohol through secondary-cleaned is sent to synthetic oil system;
(6) when detecting that the decontamination effect improving of 2# scavenging tower reaches the low point value of setting, then stop the charging of 2# scavenging tower, whole material benzenemethanol all enters 1# scavenging tower and purifies, methyl alcohol after purification is sent to synthetic oil system, carry out the replacing of acidic ion exchange resin in 1# scavenging tower simultaneously, and according to the method for step (1), pre-treatment is carried out to the new resin changed in 1# scavenging tower, and be in stand-by state;
(7) repeating step (2) ~ (6) then can realize the continuous purification operation of the methyl alcohol as methyl alcohol neutral and alkali nitrogen content≤700ppm;
(8) carry out in process in purification, when the basic n content in material benzenemethanol being detected more than 700ppm, first material benzenemethanol is sent in preliminary cleaning tower from top and carries out preliminary cleaning, methyl alcohol neutral and alkali amount of nitrides after preliminary cleaning is lower than 700ppm, and then be sent in 1# scavenging tower or 2# scavenging tower, and repeating step (2) ~ (6) purify again, and after material benzenemethanol neutral and alkali nitrogen content is lower than 700ppm, then close charging and the discharge valve of preliminary cleaning tower, make it still be in stand-by state.
2. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that described is saturated aqueous common salt for the pretreated salt solution of resin.
3. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, it is characterized in that salt solution soaks the resin time is 15 ~ 24h.
4. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that the described mass concentration for the pretreated dilute hydrochloric acid solution of resin is 1 ~ 8wt%.
5. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that the described dilute hydrochloric acid solution resin time is 2 ~ 10h.
6. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that the feeding temperature of described material benzenemethanol is 20 ~ 60 DEG C.
7. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 6, is characterized in that the feeding temperature of described material benzenemethanol is 30 ~ 50 DEG C.
8. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that the acidic resins loaded in described preliminary cleaning tower, 1# scavenging tower and 2# scavenging tower are CT151 type or the C100E type of drift Lai Te (China) company; The D113 type that Chemical Plant of Nankai Univ. produces, D061 type or D152 type.
9. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, it is characterized in that the granularity of acidic resins in described scavenging tower is 0.5 ~ 1.5mm, its coefficient of uniformity is 1.5 ~ 2.
10. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that described methyl alcohol is 1 ~ 30h through the mass space velocity that acidic resins exchange
-1.
11. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 10, is characterized in that described methyl alcohol is 10 ~ 20h through the mass space velocity that acidic resins exchange
-1.
12. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that the low point value of described scavenging tower decontamination effect improving setting is decreasing ratio≤20% of methyl alcohol neutral and alkali nitride.
13. a kind of purification process for methanol conversion gasoline Raw methyl alcohol as claimed in claim 1, is characterized in that the methyl alcohol neutral and alkali nitrogen removal efficiency after described purification reaches 94 ~ 99%, and outlet methyl alcohol neutral and alkali nitrogen content is less than or equal to 20ppm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110386857A (en) * | 2019-08-09 | 2019-10-29 | 岳阳兴长石化股份有限公司 | A kind of HPPO device recycle methanol purification method for MTBE production |
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| JPH06157374A (en) * | 1992-11-26 | 1994-06-03 | Mitsubishi Gas Chem Co Inc | Purification of methanol and its equipment |
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| CN110386857A (en) * | 2019-08-09 | 2019-10-29 | 岳阳兴长石化股份有限公司 | A kind of HPPO device recycle methanol purification method for MTBE production |
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