CN106928008A

CN106928008A - A kind of front-end hydrogenation of methanol-to-olefins product removes alkynes method

Info

Publication number: CN106928008A
Application number: CN201511034026.9A
Authority: CN
Inventors: 张忠东; 常晓昕; 钱颖; 车春霞; 韩伟; 张峰; 苟尕莲; 梁玉龙; 刘俊涛; 郭珺; 杨珊珊; 何崇慧
Original assignee: China Petroleum and Natural Gas Co Ltd
Current assignee: China Petroleum and Natural Gas Co Ltd
Priority date: 2015-12-31
Filing date: 2015-12-31
Publication date: 2017-07-07
Anticipated expiration: 2035-12-31
Also published as: CN106928008B

Abstract

A kind of front-end hydrogenation of methanol-to-olefins product removes alkynes method, using Ti-Fe-Ni hydrogenation catalysts, by the carbon two from drying tower bottom of towe, the mixed material of carbon three in methanol-to-olefins device, selection hydrogenation is carried out into adiabatic reactor reactor.Hydrogenation catalyst is Ti-Fe-Ni systems selective hydrogenation catalyst, and carrier is high-temperature inorganic oxide, and in terms of catalyst quality 100%, catalyst contains Fe 1~8%；Ti 0.2~1.5%；Ni 0.5~1.8%.Catalyst specific surface is 10~200m²/g；Pore volume is 0.2~0.63ml/g；Wherein Fe is loaded with carrier by impregnation method, through 300 DEG C~700 DEG C roastings, is reduced at a temperature of 200~500 DEG C with the atmosphere of hydrogen and is obtained；In catalyst, Fe is mainly with α-Fe₂O₃Form is present, and contains FeNi phases.The catalyst has gentle hydrogenation activity and excellent ethylene selectivity, and ethene free of losses, " green oil " growing amount is low, and catalyst cost is far below precious metals pd catalyst.

Description

A kind of front-end hydrogenation of methanol-to-olefins product removes alkynes method

Technical field

It is hydrogenated with using Ti-Fe-Ni the present invention relates to a kind of acetylene hydrogenation method of methanol-to-olefins product, particularly one kind Catalyst agent, will contained trace acetylene, propine (MA), allene (PD) hydro-conversion be second in methanol-to-olefins product The method of alkene, propylene.

Background technology

The low-carbon alkenes such as ethene, propylene are important basic chemical raw materials, with the development of Chinese national economy, particularly The development of modern chemical industry increasingly rises to the demand of low-carbon alkene, and imbalance between supply and demand will also become increasingly conspicuous.So far, produce The important channel of the low-carbon alkenes such as ethene, propylene, be still by naphtha, the catalytic cracking of light diesel fuel (being all from oil), Cracking, as raw material resources such as the naphtha of ethylene production raw material, light diesel fuels, is faced with increasingly severe short office Face.In addition, crude oil in China import volume has accounted for half of processing total amount or so, the polyolefin with ethene, propylene as raw material in recent years Product will maintain the at a relatively high percentage of import.Therefore, development non-oil resource carrys out the technology of preparing low-carbon olefins and increasingly causes The attention of people.

The MTP techniques of methyl alcohol ethene, the MTO techniques of propylene and preparing propylene from methanol are Chemical Engineering Technologies important at present.Should Technology produces low-carbon alkene with coal or the methyl alcohol of natural gas synthesis as raw material, is development non-oil resource production ethene, propylene etc. The core technology of product.

MTO technology is the committed step in coal base alkene industrial chain, and its technological process is mainly suitably is grasping Under the conditions of work, with methyl alcohol as raw material, suitable catalyst (ZSM-5 zeolite catalyst, SAPO-34 molecular sieves etc.) is chosen, solid Pass through preparing low-carbon olefin through methanol dehydration in fixed bed and fluidized-bed reactor.According to the difference of purpose product, MTO technology Be divided into methyl alcohol ethene, propylene (methanol-to-olefin, MTO), preparing propylene from methanol (methanol-to-propylene, MTP).The representative technology of MTO techniques has AP Oil company (UOP) and Hydro company (Norsk Hydro) joint development UOP/Hydro MTO technologies, the DMTO technologies of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's autonomous innovation research and development；MTP techniques Representative technology have LURGI (Lurgi) develop Lurgi MTP technologies and the independent research of Tsing-Hua University of China FMTP skills Art.

Entirely reaction can be divided into two stages to methanol-to-olefins：Water smoking, cracking reaction stage

1. water smoking

2CH₃OH→CH₃OCH₃+H₂O+Q

2. cracking reaction stage

The catalysis that the course of reaction is mainly dehydration reaction product dimethyl ether and a small amount of unconverted material benzenemethanol and carries out is split Solution reaction, including：

Main reaction (generation alkene)：

nCH₃OH→C_nH_2n+nH₂O+Q

nCH₃OH→2C_nH_2n+nH₂O+Q

N=2 and 3 (main), 4,5 and 6 (secondary)

Any of the above olefin product is gaseous state.

Side reaction (generation alkane, aromatic hydrocarbons, oxycarbide and coking)：

(n+1)CH₃OH→C_nH_2n+2+C+(n+1)H₂O+Q

(2n+1)CH₃OH→2C_nH_2n+2+CO+2nH₂O+Q

(3n+1)CH₃OH→3C_nH_2n+2+CO₂+(3n-1)H₂O+Q

N=1,2,3,4,5 ... ...

nCH₃OCH₃→C_nH_2n-6+3H₂+nH₂O+Q

N=6,7,8 ... ...

Above product has gaseous state (CO, H₂、H₂O、CO₂、CH₄Deng alkane, aromatic hydrocarbons etc.) and solid-state (macromolecule hydrocarbon and coke) Point.

Methyl alcohol after dehydration, cracking, separating, the still second containing 5~100ppm in the ethylene feed of deethanizer overhead Alkynes, it influences the polymerization process of ethene, and causes product quality to decline, it is necessary to pass through to select method of hydrotreating to be removed.Ethene The selection hydrogenation of trace acetylene has extremely important influence to the polymerization process of ethene in material, except ensureing that it is enough that hydrogenation has Activity, have under conditions of low acetylene content good except alkynes performance, it is ensured that the acetylene content of reactor outlet is up to standard, instead The hydrogen content for answering device to export is up to standard outer, also requires that the selectivity of catalyst is excellent, can make the generation second that ethene is as few as possible Alkane, it is ensured that hydrogenation process does not bring the loss of device ethene.

The separative element of methanol-to-olefins device, at present generally using the order separation process of Lummus companies.Ethene Refined adoptable front-end hydrogenation, two kinds of techniques of back end hydrogenation.Hydrogenation reactor is front-end hydrogenation, hydrogenation reaction before being located at separative element Device is back end hydrogenation after being located at separative element.Current methanol-to-olefins device generally uses back end hydrogenation technique, will pyrolysis product The ethene isolated carries out hydrofinishing removing acetylene, and propylene does not set hydrofining reactor, the mixing group of carbon four isolated Dividing carries out selective hydrogenation and removing butadiene.But the technique has drawback, ethene, propylene are refined respectively again using first separating, Plant energy consumption is of a relatively high.Therefore, it is proposed to before separative element, set finishing reactor, separated again after removing acetylene Front-end hydrogenation process route, helps to reduce plant energy consumption, improves device economic benefit.

For front-end hydrogenation technique, the selection hydrogenation of trace acetylene mainly uses single hop in methanol-to-olefins device ethylene feed Reactor process.The volume content of each material is as follows：Acetylene 1~10ppm of 5~100ppm, CO, hydrogen using in material itself The hydrogen for containing, H₂Content is generally 1.2%~2.5%.1.5~2.5MPa of reaction pressure, 2000~10000h of air speed^-1, enter 25 DEG C~50 DEG C of temperature of mouth.Reactor content composition is complex, and concrete composition is by table 1.

The methanol-to-olefins device front-end hydrogenation technique acetylene hydrogenation reactor entrance material of table 1 is constituted

Alkynes and diolefin hydrogenate catalyst are to be supported on porous Inorganic material carrier by by noble metal such as palladium On (US4762956) that obtains.In order to increase the selectivity of catalyst, reduce the green oil that oligomerization is produced during by being hydrogenated with and led The catalyst inactivation of cause, it is the method for co-catalysis component that prior art is employed and adds such as group ib element in the catalyst： Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Cu (US3912789), or add alkali metal or alkaline-earth metal (US5488024) etc., carrier used has aluminum oxide, silica (US5856262), the loyal green stone of honeycomb (CN1176291) etc. Deng.

US5856262 is reported with the modified silica of potassium hydroxide (or barium, strontium, rubidium etc. hydroxide) as carrier, The method for preparing low in acidity palladium catalyst, in air speed 3000h^-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction 0.71%, hydrogen Under conditions of alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent With aluminum oxide as carrier, addition co-catalyst silver is acted on US4404124 with palladium, is prepared for the C2 hydrogenation catalysis of function admirable Agent.The catalyst has reduction ethane growing amount, and it is anti-that acetylene of the suppression absorption on catalyst surface carries out partial hydrogenation dimerization Should, suppress 1,3-butadiene generation, reduce green oil generation, improve ethylene selectivity, reduce oxygenatedchemicals growing amount the characteristics of, It is applied widely in ethylene industry.However, above-mentioned catalyst is prepared using infusion process, limited by preparation method System, metal dispersity is only 30% or so, and catalyst performance there is also many deficiencies, still there is further improved necessity.

CN101745389A discloses a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene, belongs to oil (natural gas) chemical products synthesize and new catalytic material technical field, be related to it is a kind of have to preparation of ethylene through selective hydrogenation of acetylene it is excellent The egg-shell catalyst of good catalytic performance.It is characterized in that with aluminum oxide (Al₂O₃) bead be carrier, using infusion process prepare activity The loaded catalyst that component palladium is distributed in eggshell type, and using Ag to eggshell type Pd/Al₂O₃Catalyst is modified.Pd is loaded It is 0.01~0.1wt% to measure, and Ag is 1~5 with Pd atomic ratios.The invention has the advantages that, the one kind for being provided is used for second Alkynes selects the egg-shell catalyst of Hydrogenation ethene, can be under the conditions of conversion of alkyne high, especially in the acetylene close to 100% During conversion ratio, ethylene selectivity high is realized.

CN201110086174.0 by adsorbing specific macromolecular compound on carrier, in carrier surface certain thickness Macromolecule wrapped layer is formed, with the compound and high molecular weight reactive of the functional base of band, being allowed to have can be complexed with active component Function base, there is complex reaction on carrier surface function base by active component, it is ensured that active component in order and height point Dissipate.Using the patented method, the specific macromolecular compound of carrier adsorption carries out chemistry by the hydroxyl and macromolecule of aluminum oxide Absorption, the amount of carrier adsorption macromolecular compound will be limited by the hydroxyl quantity of aluminum oxide；By the macromolecule of functionalization Complexing with Pd is not strong, and activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, makes Improved into catalyst cost；C2 hydrogenation catalyst is prepared using the method and also haves the shortcomings that technological process is complicated. CN2005800220708.2 discloses the selective hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material, the catalysis Agent is made up of second component selected from copper, the first component of gold, silver and selection nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium, is catalyzed in addition Agent also includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound.Catalyst calcination, make With or regeneration after form fluorite structure.Catalyst oxide total content 0.01~50%, preferably 700~850 DEG C of sintering temperature. By adding the third oxide, modified aluminas or silica support, after helping to increase catalyst choice and regenerate It is active, selectivity.The technology is still that, as active component, nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium etc. are made with copper, gold, silver, palladium etc. To help component, by the oxide modifying to carrier, the regenerability of catalyst is improved.

CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide One or several, additionally include 1~10% auxiliary agent.The inventive technique is mainly used in second in coal-to-oil industry tail gas The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, with good deep hydrogenation ability.The technology be mainly used in rich in CO and The full hydrogenation of ethene, propylene, butylene etc. in the various industrial tail gas of hydrogen, is not suitable for the selection hydrogenation of alkynes, alkadienes.

ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst, Described intermetallic compound is selected from by CoAl, CoAl₃、Co₂Al₅、Co₂Al₉、o-Co₄Al₁₃、h-Co₄Al₁₃、m-Co₄Al₁₃、 FeAl、FeAl₂、Fe₃Al、Fe₂Al₅、Fe₄Al₁₃The group of composition.Wherein preferred Fe₄Al₁₃And o-Co₄Al₁₃.Change between described metal Compound is prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead Temperature 473K is answered, after stabilization reaction 20h, o-Co₄Al₁₃Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%, Fe₄Al₁₃Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And And catalyst is prepared using heat melting method, condition is harsh.

In sum, the selective hydrogenation of low-carbon (LC) alkynes and alkadienes, mainly uses noble metal catalyst at present, for non- Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this Problem, the present invention provides a kind of new Ti-Fe-Ni series hydrocatalysts and preparation method thereof.

The content of the invention

Alkynes method, particularly a kind of Ti- are removed it is an object of the invention to provide a kind of front-end hydrogenation of methanol-to-olefins product Fe-Ni hydrogenation catalyst, by contained trace acetylene, propine (MA), allene (PD) selectivity in methanol-to-olefins product Hydrogenation, is converted into ethene, propylene, while alkene does not lose.

A kind of front-end hydrogenation of methanol-to-olefins product of the present invention removes alkynes method, and not separated methanol-to-olefins are produced Thing is added carries out selective hydrogenation into adiabatic reactor reactor, to remove alkynes therein, alkadienes, is filled in adiabatic reactor reactor There is Ti-Fe-Ni to be hydrogenated with selective hydrogenation catalyst, carrier is high-temperature inorganic oxide, in terms of catalyst quality 100, catalyst Containing Fe 1~8%, preferred content is 2~6%, Ti 0.2~1.5%, and preferred content is 0.5~1%, Ni 0.5~1.8%, Preferred content is 0.8~1.2%, and catalyst specific surface is 10~200m²/ g, preferably 30~150m²/ g, pore volume be 0.2~ 0.63ml/g, preferably 0.3~0.55ml/g, wherein Fe are loaded with carrier, through 300 DEG C~700 DEG C roastings by impregnation method Burn, reduced at a temperature of 200~500 DEG C with the atmosphere of hydrogen and be obtained；In catalyst, Fe is mainly with α-Fe₂O₃Form is present, And contain FeNi phases.Hydrogenation conditions are：30 DEG C~60 DEG C of adiabatic reactor reactor inlet temperature, reaction pressure 1.5~ 2.5MPa, 2000~15000h of volume space velocity^-1, preferred hydroconversion condition is：40 DEG C~45 DEG C of adiabatic reactor reactor inlet temperature, 1.8~2.2MPa of reaction pressure, 5000~12000h of volume space velocity^-1。

Of the present invention to use hydrogenation catalyst except alkynes method, carrier is high-temperature inorganic oxide, of the invention Key problem in technology is that, containing Fe in catalyst, and have passed through specific roasting and reduction process, to carrier and is had no special requirements, such as Can be one or more in aluminum oxide, silica, zirconium oxide, magnesia etc..But most common is also most preferably to aoxidize Aluminium or alumina series carrier, alumina series carrier refer to the complex carrier of aluminum oxide and other oxides, and wherein aluminum oxide accounts for load More than the 50% of weight such as can be aluminum oxide and silica, zirconium oxide, the compound of magnesia oxide, preferably Alumina-zirconia composite carrier, wherein alumina content is more than 60%.Aluminum oxide can be θ, α, γ type or its various crystalline substance The mixture of type, preferably α-Al₂O₃Or-the Al containing α₂O₃Mixing crystal formation aluminum oxide.

Catalyst of the present invention is impregnated respectively by preparing the maceration extract of the Fe predecessors aqueous solution, Ti, Ni predecessor aqueous solution Carrier, be aged respectively, dry, roasting, finally reduction or with its mixed solution impregnated carrier is aged, dries, roasting afterwards, finally Reduction is obtained.

Preferred condition is in preparation method of the present invention：

30~60 DEG C of dipping temperature, 10~60min of load time, 1.5~5.0,20~60 DEG C of maceration extract pH value, during ageing Between 30~120min, 400 DEG C~500 DEG C of sintering temperature, 180~300min of roasting time.

Dried in the present invention and be preferably degree intensification drying, drying temperature program setting is：

Roasting is activation process in the present invention, preferably temperature-programmed calcination, and sintering temperature program setting is：

Heretofore described catalyst can be sprayed using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly It is prepared by any one impregnation method in infusion process.

The method for preparing catalyst that the present invention recommends is comprised the following steps that：

(1) carrier is weighed after measurement carrier water absorption rate.

(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity, According to carrier water absorption rate and dipping method, dipping solution, and regulation maceration extract pH value 1.5~5.0 on request are prepared, and by solution Be heated to 30~60 DEG C it is standby.

(3) using incipient impregnation or when spraying method, the carrier that will can be weighed is put into rotary drum, adjusts rotary drum rotating speed 25~30 turns/min, it is totally turned over carrier, the maceration extract of 30~60 for preparing DEG C is poured into or sprayed with given pace It is spread across on carrier, loads 5~10min.

During using excessive infusion process, the carrier that will be weighed is placed in container, is subsequently adding 30~60 DEG C of preparation of dipping Solution, the visibly moved device of Quick shaking, liberated heat discharges rapidly in making adsorption process, and makes active component uniform load to carrier On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.

During using vacuum impregnation technology, the carrier that will be weighed is placed in cyclonic evaporator, is vacuumized, and adds 30~60 DEG C Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.

(4) catalyst for having impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.

(5) solution unnecessary after dipping is leached, is then dried using the method for temperature programming in an oven, dried Temperature program(me)：

(6) dried catalyst is calcined in Muffle furnace or tube furnace and is activated, be calcined heating schedule：

Catalyst n i components can individually be impregnated using above-mentioned steps, it is also possible to and Fe is configured to mixed solution, according to upper State step total immersion；Ti components are loaded using above-mentioned same steps, 300~700 DEG C of sintering temperature, preferably 400~500 ℃。

The active component of catalyst is mainly Fe in the present invention, can be non-precious metal catalyst, it might even be possible to without cobalt, Molybdenum, tungsten, greatly reduce cost, and catalyst cost is far below precious metals pd catalyst.

Fe elements can be with Fe, Fe in catalyst of the invention₂O₃、Fe₃O₄, the variform such as FeO exist, but wherein α- Fe₂O₃The Fe of form is higher than the content of other forms, preferably accounts for more than the 50% of Fe gross masses.Recommend containing in the present invention Ni is added in the activity composition of iron, FeNi phases are formed by treatment, contribute to the activation of hydrogen, improve catalyst activity；This hair Bright middle recommendation adds TiO in the activity composition of iron content₂, be conducive to formation, the dispersion of activation of catalyst phase, and be conducive to The stabilization of phase is activated, catalyst choice and anticoking capability is improved.

The activity composition of the activation temperature of catalyst and catalyst, content and carrier related, activated mistake in the present invention α-Fe are formd after journey₂O₃The Fe of form, and it is relatively stable, and activation temperature can not be too high；On the other hand, its activation degree is again Determine the reducing condition of catalyst, provided in the present invention in the catalyst for using still with α-Fe₂O₃The Fe of form for it is main into Point, undue reduction can influence the effect of catalyst, influence selectivity, easy coking on the contrary.

Catalyst reduction of the invention refers to that catalyst uses preceding, the catalyst hydrogen-containing gas reduction after roasting, H₂Body Product content is preferably 10~50%, 200~500 DEG C of reduction temperature, 240~360min of recovery time, and volume space velocity 100~ 500h^-1, 0.1~0.8MPa of reduction pressure；Optimum condition is to use N₂+H₂Gaseous mixture is reduced, 300~400 DEG C of reduction temperature, 200~400h of volume space velocity^-1, reduce pressure and be preferably 0.1~0.5MPa.The process is generally carried out before selective hydrogenation reaction, Preferably carry out being carried out outside i.e. selective hydrogenation reaction device outside device.

The acetylene hydrogenation method of methanol-to-olefins product of the present invention, adiabatic reactor reactor reaction bed number is preferably Single hop bed.By trace acetylene contained in material, propine (MA), allene (PD) selective hydrogenation, ethene, propylene are converted into.

The acetylene hydrogenation method of methanol-to-olefins product of the present invention, it is methanol-to-olefins to carry out selection hydrogenating materials Mixed material before separation, it is characterised in that alkynes content is low in raw material, and contain micro N₂、O₂、CO、CO₂、H₂S etc., Usually constitute for：H₂1.2~1.5%, N₂0.5~1.0%, O₂0.005~0.015%, CO 0.6~1.0%, CO₂0.2~ 0.6%, H₂S 0~0.0008%, methane 6~10%, ethane 1~2%, acetylene 0~0.01%, ethene 40~60%, propane 1.5~3%, propylene 15~40%, propine 0~0.01%, carbon 4 3~6%, more than light dydrocarbon 6~10%.

Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene loss rate is low, or even does not have There is ethylene loss, " green oil " growing amount is far below noble metal catalyst, catalyst anticoking capability is excellent.

Brief description of the drawings

Accompanying drawing 1 is methanol-to-olefins product hydrogenation technique flow chart.In figure：1-DME reactors；2-MTP reactors； 3-pre- chilling is separated；4-chilling is separated；5-level Four is compressed；6-level Four is separated；7-drying tower；8- acetylene hydrogenation adiabatic reactors Reactor；9-domethanizing column；10-dethanizer.

Accompanying drawing 2 is that the catalyst XRD spectra of embodiment 3 (deducts carrier α-Al₂O₃Background).

Accompanying drawing 3 is that the catalyst XRD spectra of comparative example 2 (deducts carrier α-Al₂O₃Background).

Accompanying drawing 4 is XRD spectra (deduction carrier α-Al after the catalyst reduction of comparative example 5₂O₃Background).

XRD determining condition：

German Brooker company D8ADVANCE X diffractometers

Tube voltage：40kV electric currents 40mA

Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s sweep limits, 25 DEG C of temperature

The wavelength of Cu K α 1, abscissa is the θ of the angle of diffraction 2 in figure, and ordinate is diffracted intensity

Symbol description in Fig. 2：

● it is α-Fe₂O₃, ▲ be FeNi, ▼ is Ti₂O。

Symbol description in Fig. 3：

● it is α-Fe₂O₃, ▲ be FeNi, ◆ it is anatase.

Symbol description in Fig. 4：

★ is Fe for α-Fe, ■₃O₄, ▼ is Ti₂O, ▲ it is Ni.

As can be seen that Fe is main with α-Fe in catalyst in Fig. 2₂O₃Form occurs, relative amount 8.10%, while having FeNi phases occur.

As can be seen that Ti is sintered with iron oxide in catalyst in Fig. 3, there is anatase phase, destroy active component point Cloth and structure, catalyst activity reduction.

Fe is main in Fig. 4 occurs in simple substance α-Fe forms, and relative amount 8.92% has a small amount of Fe₃O₄Formed.

Specific embodiment

Analysis test method：

Compare table：GB/T-5816

Pore volume：GB/T-5816

Different crystal forms oxide content：XRD

Active component content：Atomic absorption method

Conversion ratio and selectivity are calculated by formula below in embodiment：

Conversion of alkyne (%)=100 × △ acetylene/entrance acetylene content

Ethylene selectivity (%)=100 × △ ethene/△ acetylene

Embodiment 1

The trifolium-shaped alpha-alumina supports 100ml of 4.5 × 4.5mm of Φ is weighed, is placed in 1000ml beakers.Take nitric acid Iron, heating for dissolving in 60ml deionized waters, adjust pH value 2.5, maceration extract temperature 50 C, incipient impregnation in carrier surface, Rapid shake carrier impregnation 6min, stands 30min to adsorption equilibrium, beaker mouthful is fully sealed with preservative film, in 60 DEG C of water-baths Ageing 30min, then in an oven according to program：Drying catalyst, Catalyst is moved into evaporating dish, activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace： Appropriate nickel nitrate is weighed, Impregnated according to above-mentioned preparation process, dried activation.Then butyl titanate is removed, is loaded according to above-mentioned same procedure, Catalyst is obtained after activation.

Evaluation method：

Catalyst is reduced, 400 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 40% hydrogen+60% 0.5MPa, recovery time 4h.Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction raw materials composition such as table 2.

The raw material of table 2 is constituted

Reaction condition：Air speed 10000h^-1, pressure 2.0MPa, 40 DEG C of reaction temperature.Reaction result is as shown in table 3, catalyst And carrier physical property is as shown in table 4.

Embodiment 2

At 50 DEG C, by NaAlO₂Solution and ZrCl₄Solution stirring mixing, is then neutralized with salpeter solution, stirs 10h, coprecipitated Form sediment the uniform Al-Zr particles of generation.Product is filtered, Na therein is washed with deionized⁺And Cl^-Ion, is subsequently adding matter Amount concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C dry 2h, and 650 DEG C of roasting 4h obtain Zr-Al and answer Carrier is closed, aluminum oxide and zirconium oxide mass ratio are 4 in carrier:1.

Complex carrier 100ml is weighed, is placed in 1000ml large beakers.Ferric nitrate and nickel nitrate are taken, heating for dissolving is in 100ml deionized waters In, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, shake beaker dipping 10min, and unnecessary maceration extract is filtered, Catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program： Drying catalyst, evaporating dish is moved into by catalyst, and activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey Sequence： Titanium tetrachloride is taken, is loaded according to above-mentioned same steps, roasting obtains catalyst.

Catalyst is reduced, 300 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 30% hydrogen+60% 0.5MPa, recovery time 4h.Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction raw materials composition is as shown in table 2.Reaction condition：Air speed 8000h^-1, pressure 1.5MPa, 50 DEG C of reaction temperature.

As shown in table 3, catalyst and carrier physical property are as shown in table 4 for reaction result.

Embodiment 3

Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Take ferric nitrate to be dissolved in 40ml deionized waters, adjust pH Value 3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and 10min is loaded in rotary drum makes active component upload uniformly, load Process control is completed in 6min, then in an oven according to program：Drying Catalyst, evaporating dish is moved into by catalyst, and activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace： A leaching is obtained to urge Agent.

Using first step same procedure, nickel nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried, be calcined, Obtain final catalyst.Drying program： Calcination procedure： Take titanium tetrachloride, Loaded according to above-mentioned same steps, roasting obtains catalyst.

Catalyst is reduced, 350 DEG C of reduction temperature, pressure 0.5MPa in reduction furnace using preceding with 20% hydrogen, also Former time 4h.Reduction rear catalyst XRD analysis are as shown in Figure 2.

Reaction raw materials composition is as shown in table 2.Reaction condition：Air speed 6000h^-1, pressure 2.5MPa, 40 DEG C of reaction temperature.

Embodiment 4

Ball-aluminium oxide-the titanium dioxide carrier of the Φ 2.0mm of 50ml is weighed, is placed in rotary evaporator.Take ferric nitrate molten Solution is in 15ml deionized waters, and regulation pH value 3.5 is standby.Rotary evaporator vacuum pumping pump is opened, to vacuum 0.1mmHg, so The maceration extract for preparing is slowly added to from charge door afterwards, 5min is added, rotation is evaporated to catalyst table under 60 DEG C of heating water baths Face mobile moisture is wholly absent, and completes load, and the catalyst that will have been loaded removes rotary evaporator, in an oven according to program： Drying, in Muffle furnace according to： Roasting.Obtain a leaching catalyst.

Lanthanum nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, obtain final catalyst.Dry journey Sequence：Calcination procedure： Take butyl titanate, Loaded according to above-mentioned same steps, roasting obtains catalyst.

Catalyst is reduced, 600 DEG C of reduction temperature, pressure 0.5MPa in reduction furnace using preceding with 15% hydrogen, also Former time 4h.Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction raw materials composition is as shown in table 2.Reaction condition：Air speed 4000h^-1, pressure 1.8MPa, 45 DEG C of reaction temperature.

Embodiment 5

The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using the same procedure of embodiment 3.Activation temperature 500℃。

Catalyst is reduced, 550 DEG C of temperature, pressure 0.5MPa, during reduction in reduction furnace using preceding with 25% hydrogen Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction condition：Air speed 13000h^-1, pressure 2.5MPa, 30 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.

Embodiment 6

Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are pressed according to aluminum oxide：Silica：Zirconium oxide =8:1:3 ratios are well mixed, then the extruded moulding on banded extruder, 120 DEG C of dryings, and 550 DEG C of roasting 3h, obtain in Muffle furnace To Zr-Si-Al composite oxide carriers.Catalyst is prepared using the same procedure of embodiment 4.

Using preceding, with the nitrogen of 45% hydrogen+55% in reduction furnace, 450 DEG C of temperature, pressure 0.5MPa is activated catalyst Time 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction condition：Air speed 5000h^-1, pressure 2.5MPa, 40 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.

Comparative example 1

Φ 4.0mm alumina supports are taken, specific surface is 4.5m²/ g, pore volume is 0.32ml/g.Using equi-volume impregnating, By on silver nitrate solution incipient impregnation to carrier, ageing-dry-roasting obtains a leaching catalyst, then that palladium bichloride is molten Solution, incipient impregnation, ageing-dry-roasting obtains final catalyst (petrochemical industry research institute PAH-01 hydrogenation catalysts).Catalysis Agent Pd contents are that 0.050%, Ag contents are 0.20%.

Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h at 100 DEG C^-1.Added with accompanying drawing 1 Suo Shi Hydrogen flow, Catalyst packing is in adiabatic bed reaction device.

Reaction condition：Air speed 10000h^-1, pressure 1.5MPa, 35 DEG C of reaction temperature.

Comparative example 2

Carrier is made with Φ 4.0mm aluminum oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1 850℃。

Catalyst is reduced, 450 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 25% hydrogen Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.Reduce the XRD diffraction spectras of rear catalyst Figure is as shown in Figure 3.

Reaction condition：Air speed 8000h^-1, pressure 2.0MPa, 40 DEG C of reaction temperature.

Reaction raw materials composition is as shown in table 2.As shown in table 3, catalyst and carrier physical property are as shown in table 4 for reaction result.

Comparative example 3

The aluminum oxide for weighing Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 450 DEG C Change.

Catalyst is reduced, 450 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 45% hydrogen Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction condition：Air speed 3000h^-1, pressure 1.5MPa, 50 DEG C of reaction temperature.

Comparative example 4

Catalyst is prepared using the identical method of embodiment 1, is directly driven after being activated at 450 DEG C, gone back without hydrogen It is former.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.

Reaction condition：Air speed 8000h^-1, pressure 2.5MPa, 50 DEG C of reaction temperature.

Comparative example 5

Catalyst is prepared using the identical method of embodiment 1, in 450 DEG C of activation.

Catalyst is reduced in tube furnace, and atmosphere is the nitrogen of 30% hydrogen+55%, 850 DEG C of temperature, pressure 0.5MPa, soak time 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.It is catalyzed after reduction The XRD diffraction spectrograms of agent are as shown in Figure 4.

Reaction condition：Air speed 8000h^-1, pressure 2.0MPa, 70 DEG C of reaction temperature.

The catalyst methanol-to-olefins product of table 3 selection hydrogenation result

The embodiment of table 4 and comparative example catalyst physical property

Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention The protection domain of the claims in the present invention should all be belonged to.

Claims

1. a kind of front-end hydrogenation of methanol-to-olefins product removes alkynes method, by the carbon from drying tower bottom of towe in methanol-to-olefins device 2nd, the mixed material of carbon three, selection hydrogenation is carried out into adiabatic reactor reactor, to remove trace acetylene therein, it is characterised in that： Before adiabatic reactor reactor for being hydrogenated with is located at domethanizing column or dethanizer, selected equipped with Ti-Fe-Ni in adiabatic reactor reactor Hydrogenation catalyst is selected, carrier is high-temperature inorganic oxide, in terms of catalyst quality 100%, catalyst contains Fe 1~8%, excellent Content being selected for 2~6%, Ti 0.2~1.5%, preferred content is 0.5~1%, Ni 0.5~1.8%, preferred content is 0.8~ 1.2%, catalyst specific surface is 10~200m²/ g, preferably 30~150m²/ g, pore volume be 0.2~0.63ml/g, preferably 0.3~ 0.55ml/g, wherein Fe are loaded with carrier by impregnation method, through 300 DEG C~700 DEG C roastings, are existed with the atmosphere of hydrogen Reduced at a temperature of 200~500 DEG C and be obtained；In catalyst, Fe is mainly with α-Fe₂O₃Form is present, and contains FeNi phases；Hydrogenation Reaction condition is：30 DEG C~60 DEG C of adiabatic reactor reactor inlet temperature, 1.5~2.5MPa of reaction pressure, volume space velocity 2000~ 15000h^-1, preferred hydroconversion condition is：40 DEG C~45 DEG C of adiabatic reactor reactor inlet temperature, 1.8~2.2MPa of reaction pressure, 5000~12000h of volume space velocity^-1。

2. it is according to claim 1 except alkynes method, it is characterised in that in catalyst, α-Fe₂O₃The Fe of form will account for the total matter of Fe More than the 50% of amount.

3. according to claim 1 except alkynes method, it is characterised in that the carrier of catalyst be aluminum oxide, or aluminum oxide and its The complex carrier of his oxide, best aluminum oxide accounts for more than the 50% of carrier quality, and other oxides can be silica, oxidation The preferred alumina-zirconia composite carrier of complex carrier of zirconium, magnesia or titanium oxide, aluminum oxide and other oxides；Oxidation Aluminium can be θ, α, γ type, preferably α-A₂O₃。

4. it is according to claim 1 except alkynes method, it is characterised in that the impregnation method is incipient impregnation, excessive leaching Stain, surface are sprayed, vacuum impregnation or repeatedly dipping.

5. according to claim 1 except alkynes method, it is characterised in that catalyst be by prepare predecessor containing the Fe aqueous solution, The Ni predecessors aqueous solution, the Ti predecessor aqueous solution, impregnated carrier, respectively ageing, dry, roasting, finally restore acquisition respectively Or to be aged after its mixed solution impregnated carrier, dried, be calcined, finally restore acquisition.

6. according to claim 5 except alkynes method, it is characterised in that：30~60 DEG C of dipping temperature, dip time 10~ 60min, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time, 300 DEG C of sintering temperature~ 700 DEG C, preferably 400~500 DEG C, 180~300min of roasting time.

7. according to claim 5 except alkynes method, it is characterised in that：Dry is degree intensification drying, drying temperature program It is set as：

8. alkynes method is removed according to claim 1 or 5, it is characterised in that：It is roasted to degree intensification roasting, sintering temperature journey Sequence is set as：

9. alkynes method is removed according to claim 1 or 5, it is characterised in that：Catalyst reduction refers to that catalyst uses preceding, roasting Catalyst after burning is reduced with hydrogen-containing gas, H₂Volume content is preferably 10~50%, 200~500 DEG C of reduction temperature, during reduction Between 240~360min, 100~500h of volume space velocity^-1, 0.1~0.8MPa of reduction pressure；Optimum condition is to use N₂+H₂Gaseous mixture Reduced, 300~400 DEG C of reduction temperature, 200~400h of volume space velocity^-1, reduce pressure and be preferably 0.1~0.5MPa.

10. it is according to claim 1 except alkynes method, it is characterised in that adiabatic reactor reactor reaction bed number is single hop bed.

11. is according to claim 1 except alkynes method, carries out the raw material of acetylene hydrogenation for not separated methanol-to-olefins are produced Thing, raw material volume composition is mainly：H₂1.2~1.5%, N₂0.5~1.0%, O₂0.005~0.015%, CO 0.6~ 1.0%, CO₂0.2~0.6%, H₂S 0~0.0008%, methane 6~10%, ethane 1~2%, acetylene 0~0.01%, ethene 40~60%, propane 1.5~3%, propylene 15~40%, propine 0~0.01%, carbon 4 3~6%, more than light dydrocarbon 6~10%.