CN103418405B - Replenishment catalyst for maintaining stabilization production of acrylonitrile device - Google Patents

Replenishment catalyst for maintaining stabilization production of acrylonitrile device Download PDF

Info

Publication number
CN103418405B
CN103418405B CN201210150513.1A CN201210150513A CN103418405B CN 103418405 B CN103418405 B CN 103418405B CN 201210150513 A CN201210150513 A CN 201210150513A CN 103418405 B CN103418405 B CN 103418405B
Authority
CN
China
Prior art keywords
grams
catalyst
composition
acrylonitrile
nitrates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210150513.1A
Other languages
Chinese (zh)
Other versions
CN103418405A (en
Inventor
张顺海
吴粮华
姜家乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201210150513.1A priority Critical patent/CN103418405B/en
Publication of CN103418405A publication Critical patent/CN103418405A/en
Application granted granted Critical
Publication of CN103418405B publication Critical patent/CN103418405B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a replenishment catalyst for maintaining stabilization production of an acrylonitrile device, and mainly solves the problem in the prior art that in use processes of catalysts the activity is reduced due to loss of molybdenum. A technical scheme is used to well solve the problem, and the technical scheme is as follows: the replenishment catalyst comprises molybdenum oxide and a composition 1, wherein the composition 1 contains carrier silica and a composition having the following general formula: in atomic ratio, A[a]B[b]C[c]Bi[d]Mo[13.6]O[x], wherein A is at least one selected from the group consisting of Li, Na, K, Rb and Cs; B is at least one selected from the group consisting of Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P and Nb; and C is at least one selected from rare earth elements. The replenishment catalyst can be used in the industrial production of maintaining stabilization production of the acrylonitrile device.

Description

What maintain acrylonitrile installation steady production adds catalyst
Technical field
The present invention relates to a kind of maintain acrylonitrile installation steady production add catalyst.
Background technology
Acrylonitrile is important Organic Chemicals, and it is produced by ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people, through constantly exploring, have carried out a series of improvement.These improve and mostly relate to catalyst activity composition, focus on the collocation between catalyst activity component, improve the activity of catalyst with selective, thus reach the raising of acrylonitrile once through yield, and the raising of production load.Current fresh catalyst single-pass yield of acrylonitrile can reach more than 80%, and after commercial plant uses for a long time, catalyst activity can decline gradually, and general use is after 2 years, and catalyst single-pass yield of acrylonitrile declines more than 1 percentage point, affects device benefit.Because catalyst is expensive, whole tower is changed because of the less employing of economic cause.Industrial usual employing maintains reactivity worth by adding catalyst or carrying out regeneration to the catalyst of activity decrease.
Ammoxidation catalyst activity decrease mainly contains following reason: 1. in use procedure, some component of catalyst is if Mo is under high temperature and reaction atmosphere particularly steam effect, and distillation loss, changes catalyst formulation composition, make it deviate from optimum proportioning scope.2. in catalyst, some has the component of redox property by over reduction, as Mo, Bi, Fe oxide all can reduction in various degree.3. catalyst activity phase structure changes in the reaction gradually.4. catalyst grain size distribution changes and causes fluidized state to change.5. catalyst duct carbon distribution etc.These factors all can cause catalyst performance to decline, and for above reason, certain measures need be taked to recover catalyst activity.
CN1110193A by supplement ammonium molybdate and under nitrogen air Mixture atmosphere regenerated catalyst.US4609635 and US4052332 all adopts the method for the catalyst of activity decrease through solution impregnation then roasting containing some composition of catalyst.
Another mode maintaining acrylonitrile yield is catalyst regeneration, CN 200910056808.0 describes the method being maintained catalyst activity by regeneration, method is after supplementary corresponding molybdenum content, the roasting when temperature 550 ~ 700 DEG C, under calcination atmosphere is selected from the condition of in air, nitrogen or water vapour at least two kinds, roasting obtains regenerated catalyst, but regenerated catalyst is held time can not be lasting, affects the stable operation of process units.In addition, can only adopt reaction ex-situ regeneration, impact is produced.
The place of the present invention's acrylonitrile installation different from the past steady production is: what the invention provides a kind of maintenance acrylonitrile installation steady production newly adds catalyst, mixed oxidization molybdenum in the composition, maintains acrylonitrile yield steady in a long-term.
Summary of the invention
Technical problem to be solved by this invention causes the problem of activity decrease because molybdenum runs off during conventional art catalyst uses, and what provide a kind of maintenance acrylonitrile installation steady production newly adds catalyst.This adds the advantage that catalyst can maintain catalyst performance stabilised for a long time in Acrylonitrile Production.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of maintain acrylonitrile installation steady production add catalyst, comprise molybdenum oxide and composition 1 forms, wherein composition 1 is containing carrier silicas and the composition comprising following general formula with atomic ratio measuring:
A aB bC cBi dMo 13.6O x
In formula, A is selected from least one in Li, Na, K, Rb and Cs;
B is selected from least one in Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P and Nb;
C is selected from least one in rare earth element;
The span of a is 0.01 ~ 2.5;
The span of b is 1 ~ 15;
The span of c is 0.01 ~ 5;
The span of d is 0.01 ~ 3;
X is for meeting the oxygen atom sum in catalyst needed for each element valence;
Wherein catalyst carrier is selected from silica, aluminium oxide or its mixture, and its consumption is 30 ~ 70% by weight percentage;
Composition 1 and molybdenum oxide weight ratio are 4 ~ 98, metal molybdenum percentage by weight >=22% in additive.
In technique scheme, the value preferable range of the value preferable range of a to be the value preferable range of 0.05 ~ 1.5, b be 2.5 ~ 12, c is the value preferable range of 0.1 ~ 3.0, d is 0.1 ~ 2.5.The preferred silica of catalyst carrier, its consumption preferable range is 35 ~ 60% by weight percentage, and in additive, the value preferable range of composition 1 and molybdenum oxide weight ratio is 5 ~ 49.In additive, the value preferable range of metal molybdenum percentage by weight is >=23%.In additive, molybdenum oxide is preferably pure molybdenum trioxide, containing molybdic oxide or its mixture.
The manufacture method that the present invention adds catalyst there is no particular/special requirement, can be undertaken by well-established law.First catalyst each component is made solution, then be mixed and made into slurry with carrier, be spray-driedly shaped to microspheroidal, last roasting is made and is added carbon monoxide-olefin polymeric, then mixes with molybdenum oxide obtainedly to add catalyst.The preparation of slurry is preferably undertaken by CN1005248C method.
The raw material that manufacture the present invention adds catalyst is:
Molybdenum component molybdenum oxide in catalyst or ammonium molybdate; The molybdenum oxide molybdenum oxide not containing elementary sulfur or arsenic.
All the other each components its nitrate the most handy, oxalates, hydroxide, oxide or can be analyzed to the salt of oxide.
Raw material as carrier silicas can use Ludox, Silica hydrogel or both mixtures.If with Ludox, its quality will meet the requirement of CN1005248C.
It is 45 ~ 55% rear spraying dry that the slurry heating prepared is concentrated to solid content.Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but with better centrifugal, can ensure that the catalyst made has good size distribution.
The roasting of catalyst can be divided into two stages to carry out: the decomposition of each element salt and high-temperature roasting in catalyst.Catabolic phase temperature is preferably 200 ~ 300 DEG C, and the time is 0.5 ~ 2 hour.Sintering temperature is 500 ~ 800 DEG C, is preferably 550 ~ 700 DEG C; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two regions in a stove, in continous way rotary roasting furnace, also can complete decomposition and roasting simultaneously.Appropriate air to be passed in catalyst decomposes and roasting process, to generate Catalytic active phase, and prevent catalyst by over reduction.
Adopt the propylene of catalyst of the present invention manufacture needed for acrylonitrile, ammonia identical with other ammoxidation catalyst of use with the specification of molecular oxygen.Although the low molecule saturated hydrocarbon content in raw material propylene there is no impact to reaction, consider that density of propylene is more preferably greater than 85% (mole) from economic point of view.Ammonia fertilizer level liquefied ammonia.Reaction desired molecule oxygen can use pure oxygen, oxygen enrichment and air from technical standpoint, but from economy and the most handy air of security consideration.
The mol ratio of the ammonia and propylene that enter fluidized-bed reactor is between 0.8 ~ 1.5, is preferably 1.0 ~ 1.3.The mol ratio of air and propylene is 8 ~ 10.5, is preferably 8.8 ~ 9.8.If due to some operational reason must with higher air than time, can 11 be increased to, significant impact do not had to reaction.But from security consideration, the excess of oxygen in reacting gas can not be greater than 7% (volume), is preferably not more than 4%.
When catalyst of the present invention is used for fluidized-bed reactor, reaction temperature is 410 ~ 470 DEG C, is preferably 420 ~ 450 DEG C.Catalyst of the present invention is a kind of catalyst being applicable to high load capacity, and therefore in process units, reaction pressure can at more than 0.08MPa, such as, and 0.08 ~ 0.18MPa.If reaction pressure does not have any adverse effect lower than 0.08MPa yet, acrylonitrile yield can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.045 ~ 0.15 hour -1, be preferably 0.06 ~ 0.13 hour -1.Load is too low not only wastes catalyst, and carbon dioxide production also can be made to increase, selective decline, be disadvantageous.Load is too high does not have practical significance, because catalyst charge is very few, the heat transfer area of catalyst layer inner cooling water pipe can be made to be less than the area removed needed for reaction heat, cause reaction temperature uncontrollable.
Manufacture the Product recycling process for refining of acrylonitrile with catalyst of the present invention, available existing production technology, does not need to do any transformation.Namely the eluting gas of fluidized-bed reactor is through neutralizing tower removing unreacted ammonia, then is absorbed by whole organic product by water at low temperature.Absorbing liquid, through extractive distillation, obtains high-purity propylene nitrile product after dehydrogenation cyanic acid and processed.
According to the response characteristic of acrylonitrile fluidized-bed catalyst, molybdenum bismuth series catalysts metal molybdenum especially easily runs off, need the catalyst added high molybdenum content but still there is good catalytic activity, acrylonitrile yield is higher than 81.0%, and catalyst of the present invention, introduces molybdenum oxide and supplement molybdenum component in the catalyst of easily loss, make renewing catalyst activity, maintain acrylonitrile installation steady production, catalyst activity can remain stable for a long time under same process condition, achieves good technique effect.
The activity examination of catalyst of the present invention is carry out in the fluidized-bed reactor of 38 millimeters at internal diameter.Loaded catalyst 400 grams, reaction temperature 430 DEG C, reaction pressure 0.084MPa, pulp furnish (mole) is propylene: ammonia: air=1: 1.25: 9.7, and the propylene load (WWH) of catalyst is 0.085 hour -1.
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The supplied propylene of reaction
Propylene conversion (%)= × 100
Propylene feed molal quantity
Generate acrylonitrile molal quantity
Acrylonitrile selectivity (%)= × 100
The supplied propylene of reaction
Generate acrylonitrile molal quantity
Acrylonitrile once through yield (%)= × 100
Propylene feed molal quantity
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
1.4 grams of NaOH and 3.6 grams of potassium hydroxide and the 11 grams of also rear dissolvings of heating that add water, obtain material (A); 846.0 grams of ammonium molybdates are dissolved in 800 grams of 60 ~ 90 DEG C of hot water, obtain material (B); By 111.1 grams of bismuth nitrates, 124.8 grams of manganese nitrates, 517.6 grams of nickel nitrates, 287.6 grams of ferric nitrates, 135.5 grams of magnesium nitrate mixing, add water 340 grams, as material (C) after heating for dissolving, take 60.7 grams of praseodymium nitrates and 21.4 grams of chromic nitrates, add water 15 grams, obtain material (D).
The Ludox being 40% by material (A) and 2500 gram weight concentration mixes, under agitation add material (B), (C) and (D) successively, slurry is obtained after fully stirring, the slurry made carried out in spray dryer framboid according to well-established law shaping, last is 89 millimeters at internal diameter, length be in the rotary roasting furnace of 1700 millimeters (φ 89 × 1700 millimeters) in 590 DEG C of roastings 2.0 hours, make and consist of:
50%K 0.15Na 0.1Fe 2.0Ni 5.0Mn 1.0Mg 1.5Cr 0.6Pr 0.4Bi 0.65Mo 13.6O x＋50%SiO 2。
Composition and MoO in additive 3part by weight is 90/10.
[embodiment 2 ~ 6 and comparative example 1 ~ 4]
What adopt method substantially the same manner as Example 1 preparation to have a different composition in following table adds catalyst, and under following reaction condition, carries out with obtained catalyst the reaction that ammoxidation of propylene generates acrylonitrile, the results are shown in Table 1.
The reaction condition of above-described embodiment and comparative example is:
φ 38 millimeters of fluidized-bed reactors
Reaction temperature 430-440 DEG C
Reaction pressure 0.084MPa
Loaded catalyst 400 grams
Catalyst propylene load (WWH) 0.085 hour -1
Pulp furnish (mole) C 3 =/ NH 3/ air=1/1.25/9.7
Table 1

Claims (1)

1. what maintain acrylonitrile installation steady production adds a catalyst, comprises molybdenum oxide and composition 1 forms, and wherein composition 1 is containing carrier silicas and the active component comprising following general formula with atomic ratio measuring:
K 0.15Na 0.1Fe 2.0Ni 5.0Mn 1.0Mg 1.5Cr 0.6Pr 0.4Bi 0.65Mo 13.6O x
X is for meeting the oxygen atom sum in catalyst needed for each element valence;
Described in composition 1, carrier accounts for 50%, and described active component accounts for 50%;
The preparation process of described catalyst is as follows:
1.4 grams of NaOH and 3.6 grams of potassium hydroxide and the 11 grams of also rear dissolvings of heating that add water, obtain material A; 846.0 grams of ammonium molybdates are dissolved in 800 grams of 60 ~ 90 DEG C of hot water, obtain material B; By 111.1 grams of bismuth nitrates, 124.8 grams of manganese nitrates, 517.6 grams of nickel nitrates, 287.6 grams of ferric nitrates, 135.5 grams of magnesium nitrate mixing, add water 340 grams, as material C after heating for dissolving, take 60.7 grams of praseodymium nitrates and 21.4 grams of chromic nitrates, add water 15 grams, obtain material D;
The Ludox being 40% by material A and 2500 gram weight concentration mixes, under agitation add material B, C and D successively, slurry is obtained after fully stirring, the slurry made carried out in spray dryer framboid according to well-established law shaping, last is 89 millimeters at internal diameter, length be in the rotary roasting furnace of 1700 millimeters in 590 DEG C of roastings 2.0 hours, obtain composition 1;
By described composition 1 and MoO 3weight ratio according to 90/10 is mixed to get described catalyst;
When described catalyst synthesizes for acrylonitrile under following process conditions, acrylonitrile yield is 81.2%:
Employing internal diameter is the fluidized-bed reactor of 38 millimeters, loaded catalyst 400 grams, reaction temperature 430 DEG C, reaction pressure 0.084MPa, and raw material composition is propylene with molar ratio computing: ammonia: air=1: 1.25: 9.7, the propylene load of catalyst is 0.085 hour -1.
CN201210150513.1A 2012-05-16 2012-05-16 Replenishment catalyst for maintaining stabilization production of acrylonitrile device Active CN103418405B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210150513.1A CN103418405B (en) 2012-05-16 2012-05-16 Replenishment catalyst for maintaining stabilization production of acrylonitrile device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210150513.1A CN103418405B (en) 2012-05-16 2012-05-16 Replenishment catalyst for maintaining stabilization production of acrylonitrile device

Publications (2)

Publication Number Publication Date
CN103418405A CN103418405A (en) 2013-12-04
CN103418405B true CN103418405B (en) 2015-04-08

Family

ID=49644091

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210150513.1A Active CN103418405B (en) 2012-05-16 2012-05-16 Replenishment catalyst for maintaining stabilization production of acrylonitrile device

Country Status (1)

Country Link
CN (1) CN103418405B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923248A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 High-pressure high-load catalyst for olefin ammoxidation reaction
CN105664962A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Catalyst for preparing acrylonitrile from propylene by ammoxidation
CN106423189A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Catalyst for olefin ammoxidation reaction
CN113828323B (en) * 2020-06-24 2024-01-30 中国石油化工股份有限公司 Additional catalyst for acrylonitrile production, preparation method and application
CN113828322B (en) * 2020-06-24 2024-01-30 中国石油化工股份有限公司 Molybdenum oxide, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1172689A (en) * 1996-08-06 1998-02-11 中国石油化工总公司 Acrylonitrile fluidized bed containing rare earth metal catalyst
CN102892499A (en) * 2010-03-23 2013-01-23 伊内奥斯美国公司 Process for preparing improved mixed metal oxide ammoxidation catalysts

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882159A (en) * 1973-08-20 1975-05-06 Standard Oil Co Reactivation of molybdenum containing oxidation catalysts in fluid bed reactors
US4162234A (en) * 1974-07-22 1979-07-24 The Standard Oil Company Oxidation catalysts
US4855275A (en) * 1988-02-18 1989-08-08 The Standard Oil Company Catalyst performance improvement via separate boron addition
CN1025551C (en) * 1990-11-05 1994-08-03 中国石油化工总公司 Long-term stabilizing method for catalyst activity of acrylonitrile fluidized bed
CN1063098C (en) * 1996-08-06 2001-03-14 中国石油化工总公司 Utilizing technology for acrylonitrile fluidized bed waste catalyst
CN1086152C (en) * 1997-09-03 2002-06-12 中国石油化工总公司 Production of propylene by ammoxidation of olefins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1172689A (en) * 1996-08-06 1998-02-11 中国石油化工总公司 Acrylonitrile fluidized bed containing rare earth metal catalyst
CN102892499A (en) * 2010-03-23 2013-01-23 伊内奥斯美国公司 Process for preparing improved mixed metal oxide ammoxidation catalysts

Also Published As

Publication number Publication date
CN103418405A (en) 2013-12-04

Similar Documents

Publication Publication Date Title
CN102188981B (en) The preparation method of acrylonitrile fluidized-bed catalyst
CN103418405B (en) Replenishment catalyst for maintaining stabilization production of acrylonitrile device
CN103418406A (en) Low-temperature high-load catalyst for olefin ammoxidation reaction
CN101147868A (en) Fluid bed catalyst for acrylonitrile production
CN101992091B (en) Unsaturated nitrile fluid catalyst prepared by ammoxidation and preparation method thereof
CN101147867B (en) Fluidized bed catalyst for oxidation of propene ammonia
CN100506377C (en) Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile
CN102452954B (en) Method for increasing yield of acetonitrile in acrylonitrile production
CN102452956B (en) Method for increasing production of acetonitrile by hydrocarbon and alcohol mixed ammoxidation
CN100408172C (en) Acrylonitrile fluid bed catalyst
CN100384531C (en) Fluid-bed catalyst for ammoxidation to prepare acrylonitrile
CN103418403A (en) Low-temperature high-load catalyst for olefin ammoxidation reaction
CN101767014B (en) Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation
CN100566828C (en) The fluid catalyst of preparation acrylonitrile
CN101306372B (en) Fluid bed catalyst for acrylonitrile production
CN100381203C (en) Acrylonitrile catalyst in high yield
CN101733117B (en) High-stability fluid catalyst for producing acrylonitrile
CN100358630C (en) Fluid-bed catalyst for propylene ammoxidation to prepare acrylonitrile
CN103894203B (en) High-load catalyst for olefin ammoxidation reactions
CN100391602C (en) Fluid-bed catalyst for ammoxidation to prepare acrylonitrile
CN100398204C (en) Catalyst for producing acrylonitrile from ammoxidation of propylene
CN101811058A (en) Unsaturated nitrile fluid catalyst prepared by ammoxidation
CN100408173C (en) Acrylonitrile catalyst of containing calcium
CN100368082C (en) Fluidized bed catalyst for prodn. of acrylonitrile
CN100384530C (en) Fluid bed catalyst for producing acrylonitrile

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant